Compositions for golf balls

ABSTRACT

Golf balls comprising thermoplastic, thermoset, castable, or millable elastomer compositions are presently disclosed. These elastomer compositions comprise reaction products of polyisocyanates and telechelic polymers having isocyanate-reactive end-groups such as hydroxyl groups and/or amine groups. These elastomer compositions can be used in any one or more portions of the golf balls, such as inner center, core, inner core layer, intermediate core layer, outer core layer, intermediate layer, cover, inner cover layer, intermediate cover layer, and/or outer cover layer.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part of U.S. patent applicationSer. No. 10/194,057, filed Jul. 15, 2002 now U.S. Pat. No. 6,867,279.This application is also a continuation-in-part of co-pending U.S.patent application Ser. No. 10/859,527, filed Jun. 2, 2004, which is acontinuation-in-part of U.S. patent application Ser. No. 10/409,144,filed Apr. 9, 2003 now U.S. Pat. No. 6,958,379, which is acontinuation-in-part of U.S. patent application Ser. No. 10/228,311,filed Aug. 27, 2002, now U.S. Pat. No. 6,835,794.

FIELD OF INVENTION

The present disclosure is directed to golf balls and, more particularly,to novel reactive liquid compositions comprising dimer polyester polyolfor use in golf balls and golf ball structures formed therefrom.

BACKGROUND OF INVENTION

Golf balls can be formed from a variety of compositions. Balata, anatural or synthetic trans-polyisoprene rubber, has been used to formgolf ball covers. The softness of the balata cover allows the player toachieve spin rates sufficient to more precisely control ball directionand distance, particularly on shorter shots. However, balata covers lackthe durability required by the average golfer, and are easily damaged.Accordingly, alternative cover compositions have been developed in anattempt to provide balls with spin rates and a feel approaching those ofbalata covered balls, while also providing a golf ball with a higherdurability and overall distance.

Ionomer resins (e.g., copolymers of olefin, such as ethylene, andethylenically unsaturated carboxylic acids, such as (meth)acrylic acids,wherein the acid groups are partially or fully neutralized by metalions) have also been used as golf ball cover materials. Ionomer coversmay be virtually cut-proof, but in comparison to balata covers, theydisplay inferior spin and feel properties.

Polyurethanes and polyureas, by providing soft “feel,” have also beenrecognized as useful materials for golf ball covers. However,conventional polyurethane covers do not match ionomer covers withrespect to resilience or rebound. Unsaturated components (such asaromatic diisocyanate, aromatic polyol, and/or aromatic polyamine) usedin a polyurethane or polyurea composition may at least in part attributeto the composition's susceptibility to discoloration and degradationupon exposure to thermal and actinic radiation, such as ultraviolet (UV)light. Conventional polyurethane covers can be prone to absorption ofmoisture, which is another mechanism through which desirable physicalproperties in the cover may be compromised. Moisture passed through thecover may further deteriorate physical and performance properties of thecore.

Therefore, a continuing need remains for novel material compositionsusable in forming golf ball portions (e.g., covers) having desirableand/or optimal combination of physical and performance characteristics,such as being hydrophobic and thus resistant to moisture absorption.Compositions comprising dimer polyester polyol, such as those disclosedherein, have superior and desirable hydrophobicity and resistance tomoisture absorption, and may be suitable for forming one or moreportions of the golf ball.

SUMMARY OF INVENTION

The present disclosure is directed to a golf ball comprising a core anda layer about the core, wherein the layer may be an outer cover layer oran intermediate layer between the core and an outer cover layer.

DEFINITIONS

As used herein, the terms “araliphatic,” “aryl aliphatic,” or “aromaticaliphatic” all refer to compounds that contain one or more aromaticmoieties and one or more aliphatic moieties, where the reactablefunctional groups such as, without limitation, isocyanate groups, aminegroups, and hydroxyl groups are directly linked to the aliphaticmoieties and not directly bonded to the aromatic moieties. Illustrativeexamples of araliphatic compounds are o-, m-, and p-tetramethylxylenediisocyanate (TMXDI).

The subscript letters such as m, n, x, y, and z used herein within thestructures are understood by one of ordinary skill in the art as thedegree of polymerization (i.e., the number of consecutively repeatingunits). In the case of molecularly uniformed products, these numbers arecommonly integers, if not zero. In the case of molecularly non-uniformedproducts, these numbers are averaged numbers not limited to integers, ifnot zero, and are understood to be the average degree of polymerization.

Any numeric references to amounts, unless otherwise specified, are “byweight.” The term “equivalent weight” is a calculated value based on therelative amounts of the various ingredients used in making the specifiedmaterial and is based on the solids of the specified material. Therelative amounts are those that result in the theoretical weight ingrams of the material, like a polymer, produced from the ingredients andgive a theoretical number of the particular functional group that ispresent in the resulting polymer.

As used herein, the term “polymer” is used to refer to oligomers,adducts, homopolymers, random copolymers, pseudo-copolymers, statisticalcopolymers, alternating copolymers, periodic copolymer, bipolymers,terpolymers, quaterpolymers, other forms of copolymers, substitutedderivatives thereof, and combinations of two or more thereof. Thesepolymers can be linear, branched, block, graft, monodisperse,polydisperse, regular, irregular, tactic, isotactic, syndiotactic,stereoregular, atactic, stereoblock, single-strand, double-strand, star,comb, dendritic, and/or ionomeric.

As used herein, the term “telechelic” is used to refer to polymershaving at least two terminal reactive end-groups and capable of enteringinto further polymerization through these reactive end-groups. Reactiveend-groups disclosed herein include, without limitation, amine groups,hydroxyl groups, isocyanate groups, carboxylic acid groups, thiolgroups, and combinations thereof.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials, times and temperatures ofreaction, ratios of amounts, values for molecular weight (whether numberaverage molecular weight (“M_(n)”) or weight average molecular weight(“M_(w)”), and others in the following portion of the specification maybe read as if prefaced by the word “about” even though the term “about”may not expressly appear with the value, amount or range. Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe following specification and attached claims are approximations thatmay vary depending upon the desired properties sought to be obtained bythe present disclosure. At the very least, and not as an attempt tolimit the application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should at least be construed in lightof the number of reported significant digits and by applying ordinaryrounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the disclosure are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

For molecular weights, whether M_(n), or M_(w), these quantities aredetermined by gel permeation chromatography using polystyrene asstandards as is well known to those skilled in the art and such as isdiscussed in U.S. Pat. No. 4,739,019 at column 4, lines 2–45, which isincorporated herein by reference in its entirety.

As used herein, the terms “formed from” and “formed of” denote open,e.g., “comprising,” claim language. As such, it is intended that acomposition “formed from” or “formed of” a list of recited components bea composition comprising at least these recited components, and canfurther comprise other non-recited components during formulation of thecomposition.

As used herein, the term “cure” as used in connection with acomposition, e.g., “a curable material,” “a cured composition,” shallmean that any crosslinkable components of the composition are at leastpartially crosslinked. In certain examples of the present disclosure,the crosslink density of the crosslinkable components, i.e., the degreeof crosslinking, can range from 5% to 100% of complete crosslinking. Inother examples, the crosslink density can range from 35% to 85% of fullcrosslinking. In other examples, the crosslink density can range from50% to 85% of full crosslinking. One skilled in the art will understandthat the presence and degree of crosslinking, i.e., the crosslinkdensity, can be determined by a variety of methods, such as dynamicmechanical thermal analysis (DMTA) in accordance with ASTM E1640-99.

As used herein, the term “saturated” or “substantially saturated” meansthat the compound or material of interest is fully saturated (i.e.,contains no double bonds, triple bonds, or aromatic ring structures), orthat the extent of unsaturation is negligible, e.g. as shown by abromine number in accordance with ASTM E234-98 of less than 10, or lessthan 5.

As used herein, the term “percent NCO” or “% NCO” refers to the percentby weight of free, reactive, and unreacted isocyanate functional groupsin an isocyanate-functional molecule or material. The total formulaweight of all the NCO groups in the molecule or material, divided by itstotal molecular weight, and multiplied by 100, equals the percent NCO.

As used herein, the term “equivalent” is defined as the number of molesof a functional group in a given quantity of material, and calculatedfrom material weight divided by equivalent weight, the later of whichrefers to molecular weight per functional group. For isocyanates theequivalent weight is (4210 grams)/% NCO; and for polyols, (56100grams)/OH#.

As used herein, the term “flexural modulus” or “modulus” refers to theratio of stress to strain within the elastic limit (measured in flexuralmode) of a material, indicates the bending stiffness of the material,and is similar to tensile modulus. Flexural modulus, typically reportedin Pa or psi, is derived in accordance to ASTM D6272-02.

As used herein, the term “water vapor transmission rate” (“WVTR”) refersto the mass of water vapor that diffuses into a material of a giventhickness (e.g., 1 mm) per unit area (e.g., 1 m²) per unit time (e.g.,24 h) at a specific temperature (e.g., 38° C.) and humidity differential(e.g., 90% relative humidity). Standard test methods for WVTR includeASTM E96-00, method E, ASTM D1653-03, and ASTM F1249-01.

As used herein, the term “material hardness” refers to indentationhardness of non-metallic materials in the form of a flat slab or buttonas measured with a durometer. The durometer has a spring-loaded indentorthat applies an indentation load to the slab, thus sensing its hardness.The material hardness can indirectly reflect upon other materialproperties, such as tensile modulus, resilience, plasticity, compressionresistance, and elasticity. Standard tests for material hardness includeASTM D2240-02b. Unless otherwise specified, material hardness reportedherein is in Shore D. Material hardness is distinct from the hardness ofa golf ball portion as measured directly on the golf ball (or otherspherical surface). The difference in value is primarily due to theconstruction, size, thickness, and material composition of the golf ballcomponents (i.e., center, core and/or layers) that underlie the portionof interest. One of ordinary skill in the art would understand that thematerial hardness and the hardness as measured on the ball are notcorrelated or convertible.

As used therein, the term “compression,” also known as “ATTIcompression” or “PGA compression,” refers to points derived from aCompression Tester (ATTI Engineering Company, Union City, N.J.), a scalewell known in the art for determining relative compression of aspherical object. Compression is a property of a material as measured ona golf ball construction (i.e., on-ball property), not a property of thematerial per se.

As used herein, the term “coefficient of restitution” or “COR” for golfballs is defined as the ratio of a ball's rebound velocity to itsinitial incoming velocity when the ball is fired out of an air cannoninto a rigid vertical plate. The faster a golf ball rebounds, the higherthe COR it has, the more the total energy it retains when struck with aclub, and the longer the ball flies. The initial velocity is about 50ft/s to about 200 ft/s, and is usually understood to be 125 ft/s, unlessotherwise specified. A golf ball may have different COR values atdifferent initial velocities.

DESCRIPTION OF INVENTION

The present disclosure relates to golf equipment such as golf balls,golf clubs (drivers, putters, woods, irons, and wedges, including headsand shafts thereof), golf shoes, golf gloves, golf bags, or the likethat comprise novel polyurethane, polyurea, and/orpoly(urethane-co-urea) compositions. The components of the compositionscan be saturated, i.e., substantially free of double or triplecarbon-carbon bonds or aromatic groups, to produce light stablecompositions. Components that are unsaturated or partially saturated canalso be used.

The compositions and materials formed therefrom can at least in partform at least one portion of the golf ball chosen from inner center,core, inner core layer, intermediate core layer, outer core layer,intermediate layer, cover, inner cover layer, intermediate cover layer,outer cover layer, coating layer, discontinuous layer, wound layer,foamed layer, lattice network layer, web or net, adhesion or couplinglayer, barrier layer, layer of uniformed or non-uniformed thickness,layer having a plurality of discrete elements, and layer filled withliquid, gel, powder, and/or gas. In one example, the material is used atleast in part to form a cover layer having a thickness of 0.125 inch orless and a Shore D hardness of 20–80.

The compositions of the present disclosure typically comprise a reactionproduct of a polyisocyanate and one or more reactants. The reactionproduct may be material that is thermoplastic, thermoset, castable, ormillable. In one example, the reaction product can be a polyurethaneformed from a polyurethane prepolymer and a curative, the polyurethaneprepolymer being a reaction product of a polyol telechelic and anisocyanate. The polyol telechelic comprises at least two terminalhydroxyl end-groups that are independently primary, secondary, ortertiary. The polyol telechelic can further comprise additional hydroxylgroups that are independently located at the termini, attached directlyto the backbone as pendant groups, and/or located within pendantmoieties attached to the backbone. The polyol telechelic can beα,ω-hydroxy telechelics having isocyanate-reactive hydroxyl end-groupson opposing termini. All polyol telechelics are polyols, which alsoinclude monomers, dimers, trimers, adducts, and the like having two ormore hydroxyl groups.

In another example, the reaction product can be a polyurea formed from apolyurea prepolymer and a curative, the polyurea prepolymer being areaction product of a polyamine telechelic and an isocyanate. Thepolyamine telechelic comprises at least two terminal amine end-groupsthat are independently primary or secondary. The polyamine telecheliccan further comprise additional amine groups that are independentlyprimary or secondary, and are independently located at the termini,attached directly to the backbone as pendant groups, located within thebackbone, or located within pendant moieties that are attached to thebackbone. The secondary amine moieties may in part form single-ring ormulti-ring heterocyclic structures having one or more nitrogen atoms asmembers of the rings. The polyamine telechelic can be α,ω-aminotelechelics having isocyanate-reactive amine end groups on opposingtermini. All polyamine telechelics are polyamines, which also includemonomers, dimers, trimers, adducts, and the like having two or moreamine groups.

In a further example, the reaction product can be a poly(urethane-urea)formed from a poly(urethane-urea) prepolymer and a curative. Thepoly(urethane-urea) prepolymer can be a reaction product of anisocyanate and a blend of polyol and polyamine telechelics.Alternatively, the poly(urethane-urea) prepolymer can be a reactionproduct of an aminoalcohol telechelic and an isocyanate. Theaminoalcohol telechelic comprises at least one primary or secondaryterminal amine end-group and at least one terminal hydroxyl end-group.The polyamine telechelic can further comprise additional amine and/orhydroxyl groups that are independently located at the termini, attacheddirectly to the backbone as pendant groups, located within the backbone,or located within pendant moieties that are attached to the backbone.The secondary amine moieties may in part form single-ring or multi-ringheterocyclic structures having one or more nitrogen atoms as members ofthe rings. The aminoalcohol telechelic can be α-amino-ω-hydroxytelechelics having isocyanate-reactive amine and hydroxyl end groups onopposing termini. All aminoalcohol telechelics are aminoalcohols, whichalso include monomers, dimers, trimers, adducts, and the like having atleast one amine group and at least one hydroxyl group.

Any one or combination of two or more of the isocyanate-reactiveingredients disclosed herein can react with stoichiometrically deficientamounts of polyisocyanate such as diisocyanate to form elastomers thatare substantially free of hard segments. Such elastomers can have rubberelasticity and wear resistance and strength, and can be millable.

Polyamine telechelics have two, three, four, or more amine end-groupscapable of forming urea linkages (such as with isocyanate groups), amidelinkages (such as with carboxyl group), imide linkages, and/or otherlinkages with other organic moieties. As such, polyamine telechelics canbe reacted with polyacids to form amide-containing polyamine or polyacidtelechelics, be reacted with isocyanates to form polyurea prepolymers,and be used as curatives to cure various prepolymers. Any one or more ofthe hydrogen atoms in the polyamine telechelic (other than those in theterminal amine end-groups) may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester moieties, ethermoieties, amide moieties, urethane moieties, urea moieties,ethylenically unsaturated moieties, acetylenically unsaturated moieties,aromatic moieties, heterocyclic moieties, hydroxy groups, amine groups,cyano groups, nitro groups, and/or any other organic moieties. Forexample, the polyamine telechelics may be halogenated, such as havingfluorinated backbones and/or N-alkylated fluorinated side chains.

Any polyamine telechelics available or known to one of ordinary skill inthe art are suitable for use in compositions of the present disclosure.The M_(w) of the polyamine telechelics can be about 100–20,000, such asabout 150, about 200, about 230, about 500, about 600, about 1,000,about 1,500, about 2,000, about 2,500, about 3,000, about 3,500, about4,000, about 5,000, about 8,000, about 10,000, about 12,000, about15,000, or any M_(w) therebetween. The polyamine telechelic can compriseone or more hydrophobic and/or hydrophilic segments.

Exemplary polyamine telechelics, such as α,ω-amino telechelics, includepolyamine polyhydrocarbons (e.g., polyamine polyolefins), polyaminepolyethers, polyamine polyesters (e.g., polyamine polycaprolactones),polyamine polyamides (e.g., polyamine polycaprolactams), polyaminepolycarbonates, polyamine polyacrylates (e.g., polyaminepolyalkylacrylates), polyamine polysiloxanes, polyamine polyimines,polyamine polyimides, fatty polyamine telechelics, polyamine telechelicsderived from acid-catalyzed polyol telechelics, derivatized polyaminetelechelics, ethylenically and/or acetylenically unsaturated polyaminetelechelics, and polyamine copolymers including polyaminepolyolefinsiloxanes (such as α,ω-diaminopoly(butadiene-dimethylsiloxane) and α,ω-diaminopoly(isobutylene-dimethylsiloxane)), polyamine polyetherolefins (such asα,ω-diamino poly(butadiene-oxyethylene)), polyamine polyetheresters,polyamine polyethercarbonates, polyamine polyetheramides, polyaminepolyetheracrylates, polyamine polyethersiloxanes, polyaminepolyesterolefins (such as α,ω-diamino poly(butadiene-caprolactone) andα,ω-diamino poly(isobutylene-caprolactone)), polyamine polyesteramides,polyamine polyestercarbonates, polyamine polyesteracrylates, polyaminepolyestersiloxanes, polyamine polyamideolefins, polyaminepolyamidecarbonates, polyamine polyamideacrylates, polyaminepolyamidesiloxanes, polyamine polyamideimides, polyaminepolycarbonateolefins, polyamine polycarbonateacrylates, polyaminepolycarbonatesiloxanes, polyamine polyacrylateolefins (such asα,ω-diamino poly(butadiene-methyl methacrylate), α,ω-diaminopoly(isobutylene-t-butyl methacrylate), and α,ω-diamino poly(methylmethacrylate-butadiene-methyl methacrylate)), polyaminepolyacrylatesiloxanes, polyamine polyetheresteramides, any otherpolyamine copolymers, as well as blends thereof. Suitable polyaminetelechelics include, without limitation, those described in U.S. patentapplication Ser. Nos. 10/194,057, 10/409,144, and 10/859,527, and U.S.Pat. No. 6,835,794, the disclosures of which are incorporated herein byreference in their entirety.

An example of polyamine polyhydrocarbons has a generic structure of:R₁HN

R₃

_(x)

R₄

_(y)

R₅

_(z)NHR₂  (1)where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃, R₄, and R₅ areindependently chosen from linear, branched, cyclic (includingmonocyclic, aromatic, bridged cyclic, spiro cyclic, fused polycyclic,and ring assemblies), saturated, unsaturated, hydrogenated, and/orsubstituted hydrocarbon moieties having 1 to about 30 carbon atoms; x,y, and z are independently zero to about 200, and x+y+z≧2. R₁ and R₂ canbe linear or branched structures having about 20 carbon atoms or less,such as 1–12 carbon atoms. R₃, R₄, and R₅ can independently have thestructure C_(n)H_(m), where n is an integer of about 2–20, and m is zeroto about 40. Any one or more of the hydrogen atoms in R₁ to R₅ may besubstituted with halogens, cationic groups, anionic groups,silicon-based moieties, ester groups, ether groups, amide groups,urethane groups, urea groups, ethylenically unsaturated groups,acetylenically unsaturated groups, hydroxy groups, amine groups, or anyother organic moieties. R₁ and R₂ can be identical. At least one of R₃,R₄, and R₅ can have the structure C_(n)H_(2n), n being an integer ofabout 2–12, and x+y+z is about 5–100.

The polyamine polyhydrocarbon can have one of the following structures:H₂N

C_(n)H_(2n)

_(x)NH₂H₂N

C_(n)H_(2n)

_(x)NHR, or RHN

C_(n)H_(2n)

_(x)NHRwhere x is the chain length, i.e., 1 or greater; n is about 1–12; and Ris alkyl group having 1 to about 20, such as 1–12, carbon atoms, aphenyl group, a cyclic group, or mixture thereof.

Polyamine polyhydrocarbons are hydrophobic in general, and can providereduced moisture absorption and permeability to the resultingcompositions. Non-limiting examples of polyamine polyhydrocarbonsinclude α,ω-diamino polyolefins such as α,ω-diamino polyethylenes,α,ω-diamino polypropylenes, α,ω-diamino polyethylenepropylenes,α,ω-diamino polyisobutylenes, α,ω-diamino polyethylenebutylenes (withbutylene content of at least about 25% by weight, such as at least 50%),amine-terminated Kraton rubbers; α,ω-diamino polydienes such asα,ω-diamino polyisoprenes, partially or fully hydrogenated α,ω-diaminopolyisoprenes, amine-terminated liquid isoprene rubbers, α,ω-diaminopolybutadienes, partially and/or fully hydrogenated α,ω-diaminopolybutadienes; as well as α,ω-diamino poly(olefin-diene)s such asα,ω-diamino poly(styrene-butadiene)s, α,ω-diaminopoly(ethylene-butadiene)s, and α,ω-diaminopoly(butadiene-styrene-butadiene)s.

One group of polyamine polyhydrocarbons is polyamine polyalkyleneshaving a plurality of secondary or tertiary amine moieties, such asthose having the formula R′HN—(R—N(R′))_(n)—H, where R is the same ordifferent alkyl, aryl, aralkyl, alicyclic, cycloalkyl, and alkoxygroups; R′ is the same or different moieties chosen from hydrogen,alkyl, aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; n isabout 5 or greater, such as about 10 or greater. R and R′ canindependently have 1 to about 20 carbon atoms, such as 1–12 carbonatoms, or about 1–4 carbon atoms.

Another group of polyamine polyhydrocarbons is polyamine polydienes,which also include polyamine poly(alkylene-diene)s, as well as blendsthereof. Suitable polyamine polydienes have Mn of about 1,000–20,000,such as about 1,000–10,000, or about 3,000–6,000, and an aminefunctionality of about 1.6–10, such as about 1.8–6, or about 1.8–2. Thediene monomers can be conjugated dienes such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, and mixtures thereof. The polyaminepolydiene can be substantially hydrogenated to improve stability, suchthat at least about 90%, or at least about 95%, of the carbon-carbondouble bonds in the polydiene are hydrogenated.

The elastomer compositions of the present disclosure can be resilient.Resilience can be measured, for example, by determining the percentageof the original height to which a ½″ steel ball will rebound after beingdropped onto an immobilized ½″ thick elastomer sample from a height ofone meter. A resilient elastomer can display a rebound height percentageof greater than 60%, such as greater than about 70%, or greater thanabout 75%.

Diamino polydienes and diamino copolydienes, among other polyaminetelechelics, are capable of imparting high resiliency in thecompositions. The diamino polydiene can be diamino polybutadiene having1,4-addition of about 30–70%, such as about 40–60%. The diaminopolybutadiene can have 1,2-addition of at least about 40%, such as about40–60%. The hydrogenated diamino polybutadiene can remain liquid atambient temperature. In one example, the diamino polybutadiene can bemore than about 99% hydrogenated, having Mn of about 3,300, an aminefunctionality of about 1.92, and a 1,2-addition content of about 54%. Inanother example, the diamino polydiene can be diamino polyisoprenehaving 1,4-addition of at least about 80% and moderate glass transitiontemperature and viscosity.

One group of diamino copolydienes has a generic structure of:

where R₁ and R₂ are independently chosen from hydrogen, alkyl, aryl,aralkyl, alicyclic, cycloalkyl, and alkoxy groups; R₃ is hydrogen,linear or branched alkyl group (such as methyl or t-butyl), cyano group,phenyl group, halide, or a mixture thereof; R₄ is hydrogen, linear orbranched alkyl group, halide (such as chloride or fluoride), or amixture thereof, x and y are independently about 1–200. R₁ and R₂ can belinear or branched, having about 20 carbon atoms or less, such as 1–12carbon atoms. The y:x ratio can be about 82:18 to about 90:10. Thediamino copolydiene can be substantially hydrogenated (i.e.,substantially all of the >C═CH— or >C═CH₂moieties are hydrogenated into>CH—CH₂or >C—CH₃ moieties, respectively). One example can behydrogenated diamino poly(acrylonitrile-co-butadiene) where R₃ is cyanogroup and R₄ is hydrogen.

Polyamine polyhydrocarbons can also be derived from polyolpolyhydrocarbons through means such as amination, or reaction withaminoalcohols, amino acids, or cyclic amides. For example, polyolpolyhydrocarbons can be end-capped with 2-, 3-, and/or 4-aminobenzoicacid and the likes thereof as disclosed herein to form aminobenzoatederivatives, e.g., polymethylene-di-p-aminobenzoates.

Non-limiting examples of polyacid telechelics include polyacidpolycaprolactones and polyacid polycaprolactams having genericstructures of:

where R₃ is a linear, branched, or cyclic moiety having at least onecarbon atom, such as about 2–60 carbon atoms; Z is the same or differentmoieties chosen from —O— and —NH—; R is the same or different moietieschosen from linear or branched aliphatic, alicyclic, araliphatic, andaromatic moieties having 1–60 carbon atoms; i is about 2–10, such asabout 2–6; x is the same or different numbers of about 1–200, such as5–100; and y is the same or different numbers of 0 or 1.

Fatty polyamine telechelics include hydrocarbon polyamine telechelics,adduct polyamine telechelics, and various oleochemical polyaminetelechelics. Hydrocarbon polyamine telechelics can have an all-carbonbackbone of about 8–100 carbon atoms, such as about 10, about 12, about18, about 20, about 25, about 30, about 36, about 44, about 54, about60, and any numbers therebetween. Fatty polyamine telechelics can bederived from corresponding fatty polyacids, such as by reacting thefatty polyacids with ammonia to obtain the corresponding nitriles whichmay then be hydrogenated to form the fatty polyamine telechelics.Alternatively, fatty polyamine telechelics can also be derived fromcorresponding fatty polyol telechelics through, for example, amination,reaction with suitable amino acids or esters thereof, reaction withsuitable cyclic amides, or reaction with suitable polyamines oraminoalcohols. These fatty polyamine telechelics can be liquid.

One form of adduct polyamine telechelics can be dimer diamines, whichcan be aliphatic α,ω-diamines having relatively high molecular weight.Dimer diamines can have a dimer content of greater than about 90%, suchas greater than about 95% by weight. The dimer diamines may beunsaturated, partly hydrogenated, or completely hydrogenated (i.e.,fully saturated). Non-limiting dimer diamines can have one of thefollowing structures:

where R is the same or different moieties chosen from hydrogen, alkyl,aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; x+y and m+n areboth at least about 8, such as at least about 10, such as 12, 14, 15,16, 18, 19, or greater.

Molecular weight of fatty polyamine telechelics can be about 200–15,000,such as about 250–12,000, or about 500–5,000. Fatty polyaminetelechelics can be liquid at room temperature, having low to moderateviscosity at 25° C. (e.g., about 100–5,000 cP or about 500–3,000 cP).Fatty polyamine telechelics can have a total amine value of at least150, at least 175, at least 185, at least 250, or at least 280, aprimary amine value of at least 100, such as at least 135, at least 150,at least 165, or at least 175, and optionally a secondary amine value ofat least 100, such as at least 135. Examples are available from HumKoChemical of Memphis, Term. Fatty polyamine telechelics can be branched,such as with alkyl groups, suitable in forming soft segments, and informulating solvent-free two pack full solid polyurethane/polyureacompositions. Fluid fatty polyamine telechelics can be used as reactivediluents in solvent-borne polyurethane/polyurea compositions to achievehigher solid content. Conventional volatile solvents such as xylene,butyl acetate, methoxy propylacetate, ethoxy propylacetate may be usedin blends thereof.

Polyamine telechelics can be derived from corresponding polyacids, suchas by reacting the polyacids with ammonia to obtain the correspondingnitriles which may then be hydrogenated to form the polyaminetelechelics. Polyamine telechelics can also be derived fromcorresponding polyol telechelics through, for example, amination,reaction with suitable amino acids or esters thereof, reaction withsuitable cyclic amides, or reaction with suitable polyamines oraminoalcohols. Amination, as understood by one of ordinary skill in theart, includes reductive amination of polyether polyols with ammonia andhydrogen in the presence of a catalyst, hydrogenation of cyanoethylatedpolyols, amination of polyol/sulfonic acid esters, reacting polyols withepichlorohydrin and a primary amine, and any other methods known to theskilled artisan. Fatty polyacids and polyacid adducts such as thedimerized fatty acids as disclosed herein can be converted to fattypolyamines and dimer diamines through one or more of these mechanisms.

In one example, the derived polyamine telechelic can be a polyaminepolyetherester having a generic structure of:

where R′₁, R₂, and Z′ are as described above, R is chosen from hydrogen,linear or branched alkyl group (such as methyl), phenyl group, halide,and mixture thereof, n is about 1–12, and x is about 1–200. Suchpolyamine polyetheresters can be obtained by end-capping polyolpolyethers with 4-aminobenzoic acid and methyl or ethyl esters thereof,e.g., poly(1,4-butanediol)-bis(4-aminobenzoate) in liquid or waxy solidform, polyethyleneglycol-bis(4-aminobenzoate), polytetramethylene etherglycol-di-p-aminobenzoate, polypropyleneglycol-di-p-aminobenzoate, andmixtures thereof.

The reactivity of the reactive amine end-groups in polyamine telechelicscan be moderated to improve molecular-stability-of theresulting-products toward actinic radiations-such as UV light, by meansof, for example, increasing steric hinderance around these amineend-groups. To impart hightened steric hinderance, the amino acids oresters of the generic structure above can have at least one branchedaliphatic or substituted cyclic structure in Z′, wherein at least onestructural condition chosen from the following is met: i) both R′₁HN andCOOR′₂ adjoin a single carbon atom; ii) R′₁HN adjoins a tertiary carbonatom in Z′, iii) R′₁HN adjoins a secondary carbon atom (such as amethine carbon) in Z′, the secondary carbon being further adjoined totwo other carbon atoms selected from tertiary and quaternary carbons;and iv) R′₁HN adjoins a secondary carbon atom in Z′, the secondarycarbon being further adjoined to a quaternary carbon atom that adjoinsCOOR′₂. Generic structures of such amino acids or esters thereof includethe following:

where R′₁ and R′₂ are as described above; R₁, R₂, R₄, and R₅ areindependently chosen from linear or branched C₁ to C₆₀ organic moieties,such as C₁ to C₂₀ aliphatic hydrocarbon moieties, or C₁ to C₁₂ alkylgroups; R₃ is linear or branched C₁ to C₆₀ organic moiety, such as C₁ toC₂₀ aliphatic hydrocarbon moiety, or C₁ to C₁₂ alkylene moiety; R₆ andR₇ are the same or different linear or branched, substituted orunsubstituted, organic moieties having about 20 carbon atoms or less,such as C₁ to C₁₂ aliphatic hydrocarbon moieties, or C₁ to C₄ alkylenemoieties; and x, y, and z are independently 0 or 1. R′₁, and R₁ to R₇may independently be linear or branched, substituted (such ashalogenated) or unsubstituted, have one or more heteroatoms such as O,N, S, P, or Si, and/or have one or more cyclic structures. Suitablecyclic structures can be substituted or unsubstituted, saturated orunsaturated, having five or more ring members, three or more of whichcan be carbon atoms, and include monocyclics, polycyclics (fused, spiro,and/or bridged), and heterocyclics. A non-limiting example of suitableamino-acids is 1-aminocyclopentane carboxylic acid.

One group of polyamine telechelics can be derived from the derivatizedpolyol telechelics as disclosed herein, thereby having ring-openedcyclic ether moieties at the termini attaching to the amine end-groups.General structure of such telechelics can beR₁HN—(Y—O)_(m)—X—O—(Z-O)_(n)—NHR₂, where R₁ and R₂ are independentlychosen from hydrogen, alkyl, aryl, aralkyl, alicyclic, cycloalkyl, andalkoxy groups; X is the backbone of the starting polyol telechelicHO-Z-OH; Y is the organic moiety of cyclic ether

Z is the organic moiety of cyclic ether;

m and n are the same or different numbers of 0 or more, and m+n is about2–100, such as about 2–40. Y and Z can be the same or different, and canhave 2 or more carbon atoms or 5 or more carbon atoms. Y and Z canindependently have one or more heteroatoms such as O, S, N, and Si. Themolecular weight of segment Z-O can be at least about 1% by weight ofthe M_(w) of the polyamine telechelic, the latter of which can be about500–20,000, such as about 600, about 1,000, about 2,000, about 3,000,about 5,000, about 8,000, about 10,000, about 12,000, about 15,000, andany number therebetween.

Polyamines suitable for use in the present disclosure include any andall organic compounds having two, three, four, or more amine groups inthe molecule that are capable of forming urea linkages (such as withisocyanate groups) or amide linkages (such as with carboxyl group). Thepolyamine can be aromatic, araliphatic, aliphatic, alicyclic,heterocyclic, saturated or unsaturated, and include diamines, triamines,tetramines, higher polyamines, fatty polyamines, alkylene polyamines,condensate polyamines, sterically hindered polyamines, and otherpolyamines, with the amine groups independently being primary orsecondary. Depending on the number of isocyanate-reactive amine groupsbeing present, polyamines may be referred to as diamines, triamines,tetramines, and other higher polyamines.

Fatty polyamines can have in the main carbon chain at least about 8carbon atoms (including carbon atom(s) in the carboxylic acid group(s),if directly attached to the main carbon chain), such as 10, 12, 16, 18,20, 22, 28, 30, 36, 40, 44, 50, 54, or 60 carbon atoms, or any numberstherebetween. The main carbon chain can be directed attached to at leastone, such as two or more, isocyanate-reactive amine functionality, whichcan be primary and/or secondary. The fatty polyamines can be monomerdiamines, dimer diamines or trimer triamines derived from fattypolyacids disclosed herein, using textbook techniques such as byreacting the dimerized fatty acids with ammonia to obtain thecorresponding dimerized fatty nitriles which may then be hydrogenated toform the dimer diamines.

The fatty polyamines can have the formula R₁—(NH—R₂)_(x)—NH₂ where R₁ isa linear or branched-alkyl group having about 8–40 carbon atoms, such asabout 10–35 carbon atoms, or about 12–18 carbon atoms; R₂ is a divalentmoiety having 1 to about 8 carbon atoms, such as about 2–6 carbon atoms,or about 2–4 carbon atoms; and x is about 1–6, such as about 1–4. R₁ andR₂ can be linear or branched, saturated or unsaturated, or combinationthereof. R₁ can be chosen from linear decyl, dodecyl, hexadecyl andoctadecyl, R₂ can be ethylene or propylene, and x is about 1–3. Thesefatty polyamines may be prepared by conventional methods, such assequential cyanoethylation reduction reactions. Commercially availableexamples include those with R₁ being octadecyl, R₂ being propylene, andx being 1, 2 or 3 (tallow diamine, tallow triamine, and tallowtetramine, respectively), available from ExxonMobil Chemical Company ofHouston, Tex.

Conventional polyamines can be fast reacting with isocyanates. In orderto extend the pot-life of the composition and improve processability,polyamine reactivity may be moderated by sterically hinder the reactiveamine groups. For example, 4,4′-bis-(sec-butylamino)-dicyclohexylmethaneand N,N′-diisopropyl-isophorone diamine are secondary diamines havingmoderated reactivity. One or more or all of the reactable amine groupswithin the polyamine compound can be sterically hindered, so that thepolyamine compound can provide the combination of reduced reactivitytoward isocyanate groups, and improved chemical stability toward actinicradiations such as UV light.

Any polyol telechelics available or known to one of ordinary skill inthe art are suitable for use in compositions of the disclosure. Polyoltelechelic such as α,ω-dihydroxy telechelics, include polyolpolyhydrocarbons (such as polyol polyolefins), polyol polyethers, polyolpolyesters (such as polyol polycaprolactones), polyol polyamides (suchas polyol polycaprolactams), polyol polycarbonates, polyol polyacrylates(such as polyol polyalkylacrylates), polyol polysiloxanes, polyolpolyimines, polyol polyimides, fatty polyol telechelics, acid-catalyzedpolyol telechelics, carbonate transesterified polyol telechelics,derivatized polyol telechelics, ethylenically and/or acetylenicallyunsaturated polyol telechelics, and polyol copolymers including polyolpolyolefinsiloxanes (such as α,ω-dihydroxypoly(butadiene-dimethylsiloxane) and α,ω-dihydroxypoly(isobutylene-dimethylsiloxane)), polyol polyetherolefins (such asα,ω-dihydroxy poly(butadiene-oxyethylene)), polyol polyetheresters,polyol polyethercarbonates, polyol polyetheramides, polyolpolyetheracrylates, polyol polyethersiloxanes, polyol polyesterolefins(such as α,ω-dihydroxy poly(butadiene-caprolactone) and α,ω-dihydroxypoly(isobutylene-caprolactone)), polyol polyesteramides, polyolpolyestercarbonates, polyol polyesteracrylates, polyolpolyestersiloxanes, polyol polyamideolefins, polyol polyamidecarbonates,polyol polyamideacrylates, polyol polyamidesiloxanes, polyolpolyamideimides, polyol polycarbonateolefins, polyolpolycarbonateacrylates, polyol polycarbonatesiloxanes, polyolpolyacrylateolefins (such as α,ω-dihydroxy poly(butadiene-methylmethacrylate), α,ω-dihydroxy poly(isobutylene-t-butyl methacrylate), andα,ω-dihydroxy poly(methyl methacrylate-butadiene-methyl methacrylate)),polyol polyacrylatesiloxanes, polyol polyetheresteramides, any otherpolyol copolymers, as well as blends thereof. Other polyol telechelicscan be derived from polyacid telechelics through reaction with polyols,aminoalcohols, and/or cyclic ethers, or derived from polyaminetelechelics through reaction with hydroxy acids, cyclic esters, and/orcyclic ethers as disclosed herein.

The molecular weight of the polyol telechelics can be about 100–20,000,such as about 200, about 230, about 500, about 600, about 1,000, about1,500, about 2,000, about 2,500, about 3,000, about 3,500, about 4,000,about 5,000, about 8,000, about 10,000, or any number therebetween. Thepolyol telechelics can have one or more hydrophobic and/or hydrophilicsegments.

An example of polyol polyhydrocarbons has a generic structure of:HO

R₃

_(x)

R₄

_(y)

R₅

_(z)OH  (55)where R₃ to R₅ are independently chosen from linear, branched, cyclic(including monocyclic, aromatic, bridged cyclic, spiro cyclic, fusedpolycyclic, and ring assemblies), saturated, unsaturated, hydrogenated,and/or substituted hydrocarbon moieties having about 2–30 carbon atoms;x, y, and z are independently zero to about 200, and x+y+z≧2. R₃ to R₅can independently have the structure C_(n)H_(m), where n is an integerof about 2–30, and m is zero to about 60. Any one or more of thehydrogen atoms in R₃ to R₅ may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester moieties, ethermoieties, amide moieties, urethane moieties, urea moieties,ethylenically unsaturated moieties, acetylenically unsaturated moieties,aromatic moieties, heterocyclic moieties, hydroxy groups, amine groups,cyano groups, nitro groups, and/or any other organic moieties. One ormore of R₃ to R₅ can have the structure C_(n)H_(2n), n being an integerof about 2–20, and x+y+z is about 5–100.

Polyol polyhydrocarbons are hydrophobic in general, and provide reducedmoisture absorption and permeability to the elastomer compositions ofthe present disclosure. Non-limiting examples of polyol polyhydrocarbonsinclude α,ω-dihydroxy polyolefins such as α,ω-dihydroxy polyethylenes,α,ω-dihydroxy polypropylenes, α,ω-dihydroxy polyethylenepropylenes,α,ω-dihydroxy polyisobutylenes, α,ω-dihydroxy polyethylenebutylenes(with butylene content of at least about 25% by weight, such as at leastabout 50%), hydroxyl-terminated Kraton rubbers; α,ω-dihydroxy polydienessuch as α,ω-dihydroxy polyisoprenes, partially or fully hydrogenatedα,ω-dihydroxy polyisoprenes, hydroxyl-terminated liquid isoprenerubbers, α,ω-dihydroxy polybutadienes, partially and/or fullyhydrogenated α,ω-dihydroxy polybutadienes; as well as α,ω-dihydroxypoly(olefin-diene)s such as α,ω-dihydroxy poly(styrene-butadiene)s,α,ω-dihydroxy poly(ethylene-butadiene)s, and α,ω-dihydroxypoly(butadiene-styrene-butadiene)s.

The polyol polyhydrocarbons can be polyol polydienes, which also includepolyol poly(alkylene-diene)s, as well as blend thereof. Polyolpolydienes can have M_(n) of about 1,000–20,000, such as about1,000–10,000 or about 3,000–6,000, and a hydroxyl functionality of about1.6–10, such as about 1.8–6 or about 1.8–2. The diene monomers can beconjugated dienes, such as 1,3-butadiene, isoprene,2,3-dimethyl-1,3-butadiene, and mixtures thereof. The polyol polydienecan be substantially hydrogenated to improve stability, such that atleast about 90%, or at least about 95%, of the carbon-carbon doublebonds in the polyol are hydrogenated.

Unhydrogenated, partially hydrogenated, and fully hydrogenated polydienediols and copolydiene diols, among other polyol telechelics, are capableof imparting high resiliency in the compositions. The polydiene diol canbe polybutadiene diol having 1,4-addition of about 30–70%, such as about40–60%. The polybutadiene diol can have 1,2-addition of at least about40%, such as about 40–60%, so that the hydrogenated polybutadiene diolremains liquid at ambient temperature. The polybutadiene diol can bemore than about 99% hydrogenated, having M_(n) of about 3,300, ahydroxyl functionality of about 1.92, and a 1,2-addition content ofabout 54%. The polydiene diol can be a polyisoprene diol having1,4-addition of at least about 80% to reduce glass transitiontemperature and viscosity.

One group of copolydiene diols has a generic structure of:

where R₃ is chosen from hydrogen, linear and branched alkyl groups (suchas methyl), cyano group, phenyl group, halide, and mixture thereof; R₄is chosen from hydrogen, linear and branched alkyl group (such asmethyl), halide (such as chloride or fluoride), and mixture thereof; xand y are independently about 1–200. The y:x ratio can be about 82:18 toabout 90:10. The copolydiene diol can be substantially hydrogenated(i.e., substantially all of the >C═CH— or >C═CH₂ moieties arehydrogenated into >CH═CH₂— or >C—CH₃ moieties, respectively). Oneexample is hydrogenated poly(acrylonitrile-co-butadiene) diol, where R₃is cyano group, and R₄ is hydrogen.

An example of the polyol polyesters has a generic structure of:

where R₃ to R₉ are independently chosen from linear, branched, andcyclic moieties having 1 to about 60 carbon atoms; Z is the same ordifferent moieties chosen from —O— and —NH—; i is about 2–10, such asabout 2–6; x is about 1–200, and y and z are independently zero to about200. The number x can be the same or different numbers. R₃ to R₉ canindependently have the structure C_(n)H_(m), where n is an integer ofabout 2–30, and m is an integer of about 2–60. Any one or more of thehydrogen atoms in R₃ to R₉ may be substituted with halogens, cationicgroups, anionic groups, silicon-based moieties, ester groups, ethergroups, amide groups, urethane groups, urea groups, ethylenicallyunsaturated groups, acetylenically unsaturated groups, amine groups,hydroxyl groups, or any other organic moieties. R₃ and R₆ can beidentical, having a structure C_(n)H_(2n), n being an integer of about2–30, x+y+z is about 1–100, such as about 5–50.

The polyol polyester can have a crystallization enthalpy of at mostabout 70 J/g and M_(n) of about 1,000–7,000, such as about 1,000–5,000.This polyol polyester can be blended with a polyol polyether havingM_(n) of about 500–2,500. The average hydroxyl functionality of theblend, which is the ratio of total number of hydroxyl groups in theblend to total number of telechelic molecules in the blend, can be about2–2.1. The polyol polyester can have an ester content (number of esterbonds/number of all carbon atoms) of about 0.2 or less, such as about0.08–0.17.

The polyester chain can be formed from condensation polymerizationreaction of polyacids and/or anhydrides with excess polyols.Alternatively, the polyester chain can be formed at least in part fromring-opening polymerization of cyclic esters. The polyester chain canalso be formed at least in part from polymerization of hydroxy acids,including those that structurally correspond to the cyclic esters.Obviously, the polyester chain can comprise multiple segments formedfrom polyacids, anhydrides, polyols, cyclic esters, and/or hydroxyacids, non-limiting examples of which are disclosed herein. Suitablereactants also include polyacid telechelics, polyol telechelics, andhydroxy acid polymers. In one example, at least one polyacid, anhydride,polyol, cyclic ester, or hydroxy acids having M_(w) of at least about200, such as at least about 400, or at least about 1,000, is used toform the polyester chain. In another example, the polyester chain has 1to about 100 ester linkages, such as about 2–50, or about 2–20.

The polyol polyesters can be formed from the condensation of one or morepolyols having about 2–18 carbon atoms, such as about 2–6 carbon atoms,with one or more polycarboxylic acids or their anhydrides having fromabout 2–14 carbon atoms. Non-limiting examples of polyols includeethylene glycol, propylene glycol such as 1,2-propylene glycol and1,3-propylene glycol, glycerol, pentaerythritol, trimethylolpropane,1,4,6-octanetriol, butanediol, pentanediol, hexanediol, dodecanediol,octanediol, chloropentanediol, glycerol monoallyl ether, glycerolmonoethyl ether, diethylene glycol, 2-ethylhexanediol-1,4,cyclohexanediol-1,4, 1,2,6-hexanetriol, neopental glycol,1,3,5-hexanetriol, 1,3-bis-(2-hydroxyethoxy)propane and the like. Cyclicethers having about 2–18 carbon atoms may be used in place of or inaddition to the polyols. Non-limiting examples of polycarboxylic acidsinclude phthalic acid, isophthalic acid, terephthalic acid,tetrachlorophthalic acid, maleic acid, dodecylmaleic acid,octadecenylmaleic acid, fumaric acid, aconitic acid, trimellitic acid,tricarballylic acid, 3,3′-thiodipropionic acid, succinic acid, adipicacid, malonic acid, glutaric acid, pimelic acid, sebacic acid,cyclohexane-1,2-dicarboxylic acid, 1,4-cyclohexadiene-1,2-dicarboxylicacid, 3-methyl-3,5-cyclohexadiene-1,2-dicarboxylic acid and thecorresponding acid anhydrides, acid chlorides and acid esters such asphthalic anhydride, phthaloyl chloride and the dimethyl ester ofphthalic acid.

Examples of polyol polyesters include, without limitation, poly(ethyleneadipate) diols, poly(butylene adipate) diols, poly(1,4-butyleneglutarate) diols, poly(ethylene propylene adipate) diols, poly(ethylenebutylene adipate) diols, poly(hexamethylene adipate) diols,poly(hexamethylene butylene adipate) diols, poly(hexamethylenephthalate) diols, poly(hexamethylene terephthalate) diols,poly(2-methyl-1,3-propylene adipate) diols, poly(2-methyl-1,3-propyleneglutarate) diols, and poly(2-ethyl-1,3-hexylene sebacate) diols.Non-limiting examples of polyester polyols based on fatty polyacids orpolyacid adducts, such as those disclosed herein, include poly(dimeracid-co-ethylene glycol) hydrogenated-diols and poly(dimeracid-co-1,6-hexanediol-co-adipic acid) hydrogenated diols.

An example of the polyol polycaprolactones has a generic structure of:

where R₃, Z, i, x are as described above. The number x can the same ordifferent, and can be about 5–100. Suitable polycaprolactone polyolsinclude, but are not limited to, polyol-initiated andpolyamine-initiated ring-opening polymerization products ofcaprolactone, and polymerization products of hydroxy caproic acid.Suitable polyol and polyamine initiators include any polyols andpolyamines available to one of ordinary skill in the art, such as thosedisclosed herein, as well as any and all of the polyol telechelics andpolyamine telechelics of the present disclosure. The caprolactonemonomer can be replaced by or blended with any other cyclic estersand/or cyclic amides as disclosed herein.

Polyamine-initiated and polyol-initiated polycaprolactone polyolsinclude, but are not limited to, bis(2-hydroxyethyl) ether initiatedpolycaprolactone polyols, 2-(2-aminoethylamino) ethanol initiatedpolycaprolactone polyols, polyoxyethylene diol initiatedpolycaprolactone polyols, propylene diol initiated polycaprolactonepolyols, polyoxypropylene diol initiated polycaprolactone polyols,1,4-butanediol initiated polycaprolactone polyols,trimethylolpropane-initiated polycaprolactone polyols,hexanediol-initiated polycaprolactone polyols, polytetramethylene etherdiol initiated polycaprolactone polyols, bis(2-aminoethyl)amineinitiated polycaprolactone polyols, 2-(2-aminoethylamino) ethylamineinitiated polycaprolactone polyols, polyoxyethylene diamine initiatedpolycaprolactone polyols, propylene diamine initiated polycaprolactonepolyols, polyoxypropylene diamine initiated polycaprolactone polyols,1,4-butanediamine initiated polycaprolactone polyols, neopentyl diamineinitiated polycaprolactone polyols, hexanediamine-initiatedpolycaprolactone polyols, polytetramethylene ether diamine initiatedpolycaprolactone polyols, and mixtures thereof.

Fatty polyol telechelics include adduct polyol telechelics and variousoleochemical polyol telechelics. Fatty polyol telechelics can have anall-carbon backbone of about 8–100 carbon atoms, such as about 10, about12, about 18, about 20, about 25, about 30, about 36, about 44, about54, about 60, and any numbers therebetween. Oleochemical polyoltelechelics are often derived from natural fats and oils which, if nothaving hydroxyl groups already, can have double bonds and/or carboxylgroups that may he converted into hydroxyl-groups. Double bonds-on-fattyacids can be epoxidized by hydrogen peroxide to form multiple oxiranefunctionalities. These epoxidized fats and oils can be liquid at ambienttemperature, and can be used as phthalate-free, non-volatile, extractionand migration resistant plasticizers/stabilizers, as polymer buildingblocks for non-urethane compositions (e.g., linoleum, syntheticleather), or as crosslinking agents for hydroxyl and/orcarboxyl-terminated polymers (e.g., polyesters, polyurethane,polyacrylate resins). They can be reacted with low molecular weightmono- and/or polyfunctional alcohols, acids, and/or or hydroxy acids toform ether polyols and/or ester polyols, which may or may not containoxirane groups (i.e., through incomplete or complete reactions,respectively). Fatty polyol telechelics derived as such can be liquid,of relatively low molecular weight, and may have reactive hydroxylgroups in the ester positions only (i.e., fatty acid polyol esters likeglycerol monostearate), in the hydrocarbon chain only (i.e., fatty acidpolyol esters of monofunctional alcohols), or both (i.e., fatty acidpolyol esters such as ricinoleic acid monoglyceride). These fatty polyoltelechelics can be free of triglyceride ester linkages.

One form of adduct polyol telechelics can be dimer diols, which can bealiphatic α,ω-diols having relatively high molecular weight. Dimer diolscan be produced by polymerization (e.g., dimerization) of one or moremonounsaturated and/or polyunsaturated fatty monoalcohols, such aspalmitoleyl, oleyl, elaidyl, linolyl, linolenyl and/or erucyl alcohols.The resulting dimer diols can be mixtures having a major content (e.g.,greater than about 50% by weight of the mixture) of dimer diols andrelatively minor contents (e.g., less than about 30%) of the monomeralcohols, trimers, and/or higher oligomers.

Dimer diols can also be prepared from dimer diacids and/or estersthereof, including dimethylesters and hydroxy acid methylesters, such asthose disclosed herein, by means of hydrogenation or condensation withpolyols (e.g., ethylene glycols) and/or polyacids (e.g., azelaic acids).The former can yield hydrocarbon polyol telechelics, whereas the latercan yield polyol polyesters. Starting from a distilled dimer diacid,hydrogenation can produce dimer diols having a dimer content of greaterthan about 90%, such as greater than about 95% by weight. The resultingdimer diols may be unsaturated, partly hydrogenated, or completelyhydrogenated (i.e., fully saturated). Likewise, castor oil can produce,through hydrolysis, esterification or transesterification, andhydrogenation, 12-hydroxystearyl alcohol having one primary and onesecondary hydroxyl group and a relatively high molecular weight.

Non-limiting dimer diols can have one of the following structures:

where x+y and m+n are both at least about 8, such as at least about 10,such as 12, 14, 15, 16, 18, 19, or greater.

Molecular weight of fatty polyol telechelics can be about 200–15,000,such as about 250–12,000, or about 500–5,000. Fatty polyol telechelicscan be liquid at room temperature, having low to moderate viscosity at25° C. (e.g., about 100–10,000 cP or about 500–5,000 cP). It ispostulated that highly branched polyols in general has desirableresistance to hydrolysis. As such, the fatty polyol telechelics can bebranched, such as with alkyl groups, thereby displaying improvedchemical stability, improved color stability (i.e., reduced yellowingbecause of reduction or elimination of unsaturation), high mechanicalstrength and durability, suitable in forming soft segments, and informulating solvent-free two pack full solid polyurethane/polyureacompositions. Because of their fluidity, these fatty polyol telechelicscan be used as reactive diluents in solvent-borne polyurethane/polyureacompositions to achieve higher solid content. Conventional volatilesolvents such as xylene, butyl acetate, methoxy propylacetate, ethoxypropylacetate may still be necessary to improve compatibility of resinand polyisocyanate, avoid phase separation, and adjust viscosity, butthe level of these non-reactive diluents can be significantly reduced.

The polyol can have a relatively low molecular weight, such as 150, 180,300, 400, 500, 700, 800, 1,000, and any number therebetween. The polyolcan be of a single molecular species, or a blend of two or more suitablepolyol telechelics. One polyol can be present in an amount of 50–100% byweight. One or more aliphatic polyols as disclosed herein (e.g., C₃ toC₁₂ aliphatic polyols like 1,5-pentanediol, 3-methyl-1,5-pentanediol,1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol,1,10-decanediol), in an amount of 0–50% by weight, can be mixed with thefirst polyol. Small quantities of trimethylolethane, trimethylolpropane,and/or pentaerythritol may be mixed in for branching. In one example,the polyol comprises 50–100 mole % of at least a first diol and 0–50mole % of at least a second diol, both independently chosen from1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol,1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol,diethylene glycol, triethylene glycol, tetraethylene glycol, dipropyleneglycol, tetrapropylene glycol, other oligomer diols of ethylene oxideand/or propylene oxide, and other aliphatic diols.

Polyols include, but are not limited to, those described in U.S. patentapplication Ser. Nos. 10/194,057, 10/409,144, and 10/859,527, and U.S.Pat. No. 6,835,794, the disclosures of which are incorporated herein byreference in their entirety. Fatty polyols include fatty diols and fattytriols such as 1,9,10-trihydroxyoctadecane. Other non-limiting examplesinclude triols and tetraols having a molecular weight of 1,000 or less,or 500 or less, or 300 or less, preferably at least about 240, likepolycaprolactone triols.

As used herein, the term “aminoalcohol telechelic” refers to telechelicpolymers having at least one terminal amine end-group and at least oneterminal hydroxyl end-group. Any such aminoalcohol telechelics availableto one of ordinary skill in the art are suitable for use in compositionsof the present disclosure. Aminoalcohols useful in the presentdisclosure include any and all monomers, oligomers, and polymers havingat least one free isocyanate-reactive hydroxy group and at least onefree isocyanate-reactive amine group. Suitable aminoalcohol telechelicsand aminoalcohols include, without limitation, those described in U.S.patent application Ser. Nos. 10/194,057, 10/409,144, and 10/859,527, andU.S. Pat. No. 6,835,794, the disclosures of which are incorporatedherein by reference in their entirety.

As used herein, the term “polyacids” encompasses diacids, triacids,tetracids, other higher acids, as well as acid anhydrides, dianhydrides,chlorides, esters, dimers, trimers, oligomers, polymers, and any otherstructures capable of forming at least two ester or amide linkages.Suitable organic polyacids include, but are not limited to, organicmonomeric diacids having about 2–60 carbon atoms, such as branched orlinear aliphatic dicarboxylic acids having about 2–44 carbon atoms,alkane dicarboxylic acids having about 6–22 carbon atoms, cyclic orcycloaliphatic dicarboxylic acids having about 6–44 carbon atoms, andaromatic dicarboxylic acids having about 8–44 carbon atoms. Thepolyacids can be aliphatic dicarboxylic acids and alicyclic dicarboxylicacids having para-, meta- and/or ortho-positioned dicarboxylic acidmoieties.

Non-limiting examples of polyacids include unsaturated aliphaticdicarboxylic acids such as maleic acid, fumaric acid, itaconic-acid,citraconic acid, and mesaconic acid; saturated aliphatic polycarboxylicacids such as oxalic acid, malonic acid, glyceric acid, dimethyl malonicacid, succinic acid, methylsuccinic acid, diglycolic acid, glutaricacid, 3-methylglutaric acid, 2,2- and 3,3-dimethylglutaric acid, adipicacid, 2,2,4- and 2,4,4-trimethyladipic acid, pimelic acid, suberic acid,azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid,brassylic acid, tetradecanedioic acid, pentadecanedioic acid,heptadecanedioic acid, heptadecanedioic acid, octadecanedioic acid,heptadecanedicarboxylic acid, octadecanedicarboxylic acid,nonadecanedicarboxylic acid, and eicosanedicarboxylic acid; alicyclicdicarboxylic acids such as 1,1-cyclopropanedicarboxylic acid,1,3-cyclopentanedicarboxylic acid, 1,2- and 1,4-cyclohexanedicarboxylicacid, 4,4′-dicaboxydicyclohexylmethane,3,3′-dimethyl-4,4′-dicarboxydicyclohexylmethane,4,4′-dicarboxydicyclohexylpropane, 1,4-bis(carboxymethyl)cyclohexane,2,3-, 2,5-, and 2,6-norbornanedicarboxylic acid, tetrahydrophthalicacid, hexahydrophthalic acid, hexahydroterephthalic acid,hexahydroisophthalic acid, and hexahydronaphthalic acid; aromaticdicarboxylic acids such as phthalic acid, isophthalic acid,tributylisophthalic acid, terephthalic acid, nitrophthalic acid,5-methylisophtalic acid, 2-methylterephtalic acid, 2-chloroterephtalicacid, naphthalic acid, diphenic acid, 4,4′-diphenyldicarboxylic acid,4,4′-oxydibenzoic acid, and 1,3-phenylenedioxy diacetic acid;tricarboxylic acids, tetracarboxylic acids, and the like, such ashexanetricarboxylic acid, hexanetetracarboxylic acid,1,2,3,4-cyclobutanetetracarboxylic acid,2,2-dimethylcyclobutane-1,1,3,3-tetracarboxylic acid,1,2,3,4-cyclopentanetetracarboxylic acid,cis,cis-1,3,5-trimethyl-cyclohexane-1,3,5-tricarboxylic acid, aconiticacid, 1,2,3-benzenetricarboxylic acid, trimellitic acid, trimesic acid,2-methylbenzene-1,3,5-tricarboxylic acid, pyromellitic acid,3,4,3′,4′-biphenyltetracarboxylic acid,2,3,3′,4′-biphenyltetracarboxylic acid, and mellitic acid.

Non-limiting examples of acid anhydrides include aliphatic diacidanhydrides such as maleic anhydride, itaconic anhydride, and citraconicanhydride; aromatic diacid anhydrides such as phthalic anhydride.Non-limiting examples of acid dianhydrides include pyromelliticdianhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, and3,3,4,4-biphenyltetracarboxylic dianhydride. Non-limiting examples ofcarboxylic acid (co)polymers, which can have M_(n) of about1,000–15,000, include dicarboxy-terminated polybutadienes,poly(meth)acrylic acids, polyitaconic acids, copolymers of (meth)acrylicacid and maleic acid, copolymers of (meth)acrylic acid and styrene,dicarboxy-terminated poly(dimethylsiloxane-co-diacid), anddicarboxy-terminated poly(dimethylsiloxane-co-dimer acid).

The polyacid may further contain various moieties such as, but are notlimited to, heterocyclic rings, nitro groups, amine groups, iminegroups, carbonyl groups, hydroxyl groups, ether bonds, ester bonds,amide bonds, imide groups, urethane bonds, urea bonds, and/or ionicgroups. Non-limiting examples of ketodiacids are oxaloacetic acids, 2-and 3-oxoglutaric acid, and dimethyl-3-oxoglutaric acid. Non-limitingexamples of heterocyclic diacids are dinicotinic acid, dipicolinic acid,lutidinic acid, quinolinic acid, and pyrazine-2,3-dicarboxylic acid.Ionic groups can be anionic groups, such as carboxylates, sulfonates,and phosphates. Non-limiting examples are alkali metal salts ofsulfoisophthalic acid, such as sodium 3-sulfoisophthalate and potassium3-sulfoisophthalate. Other useful polyacids include salts of tri- ortetrasulfonic acids, such as trisodium salt ofnaphthalene-1,3,6-trisulfonic acid, the trisodium salt of8-tetradecyloxypyrene-1,3,6-trisulfonic acid, and the tetrasodium saltof pyrene-1,3,6,8-tetrasulfonic acid.

Fatty polyacids can be derived from monounsaturated and/orpolyunsaturated fatty acids through reactions involving the doublebonds, such as ozonolysis (e.g., forming azelaic acid from oleic acid),caustic oxidation (e.g., forming sebacic acid from ricinoleic acid orcastor oil), and polymerization (e.g., dimerization). Polymeric fattyacids can be formed from a polymerization reaction of a saturated,ethylenically unsaturated, or acetylenically unsaturated fatty acid andat least one compound to provide a second acid moiety or a functionalgroup convertible to the second acid moiety. Polymeric fatty acids mayresult from the polymerization of oils or free acids or esters thereof,via dienic Diels-Alder reaction to provide a mixture of dibasic andhigher polymeric fatty acids. In place of these methods ofpolymerization any other method of polymerization may be employed,whether the resultant polymer possesses residual unsaturation or not

Fatty acids can be long-chain monobasic fatty acids having a C₆ orlonger chain, such as C₁₁ or longer or C₁₆ or longer, and C₂₄ orshorter, such as C₂₂ or shorter. Unsaturated fatty acids and estersthereof can be monounsaturated and/or polyunsaturated, monocarboxylicand/or polycarboxylic, and include, without limitation, oleic acid,linoleic acid, linolenic acid, palmitoleic acid, elaidic acid, erucicacid, hexadecenedioic acid, octadecenedioic acid, vinyl-tetradecenedioicacid, eicosedienedioic acid, dimethyl-eicosedienedioic acid,8-vinyl-10-octadecenedioic acid, methyl, ethyl, and other esters (suchas linear or branched alkyl esters) thereof, and mixtures thereof. Alsodimerizable are fatty acid mixtures obtained in the hydrolysis ofnatural fats and/or oils, such as olive oil fatty acids, sunflower oilfatty acids, soybean fatty acids, corn oil fatty acids, canola fattyacids, cottonseed oil fatty acids, coriander oil fatty acids, tallowfatty acids, coconut fatty acids, rapeseed oil fatty acids, fish oilfatty acids, tall oil fatty acids, methyl, ethyl, and other estersthereof, and mixtures thereof.

The polymeric fatty acids can be adduct acid, such as adduct diacidformed between a conjugated ethylenically unsaturated fatty acid (e.g.,linoleic acid, soybean oil fatty acid, tall oil fatty acid) and ashort-chain unsaturated acid (e.g., acrylic acid, methacrylic acid,crotonic acid). Methods for producing such adduct acids are described,for example, in U.S. Pat. Nos. 5,136,055, 5,053,534, 4,156,095, and3,753,968. Alternatively, the polymeric fatty acid can be obtained byhydroformylating an unsaturated fatty acid and then oxidizing it intofatty dicarboxylic acid. For example, oleic acid can be reacted withcarbon monoxide and hydrogen to form 9(10)-formyloctadecanoic acid,which can then be oxidized to 9(10)-carboxyoctadecanoic acid.

Polymeric fatty acids may also be obtained in known manners (e.g.,addition polymerization using heat and a catalyst) from one monobasicfatty acid or a blend of two or more monobasic fatty acids, themonobasic fatty acids being saturated, ethylenically unsaturated, oracetylenically unsaturated. The resulting polymeric fatty acids areoften referred to in the art as dimers (i.e., dimerized fatty acids),trimers (i.e., trimerized fatty acids) and so forth (e.g., oligomericfatty acids). Saturated monobasic fatty acids can be polymerized atelevated temperatures with a peroxidic catalyst such as di-t-butylperoxide. Suitable saturated monobasic fatty acids include linear orbranched acids such as caprylic acid, pelargonic acid, capric acid,lauric acid, myristic acid, palmitic acid, isopalmitic acid, stearicacid, arachidic acid, behenic acid, and lignoceric acid.

Ethylenically unsaturated monobasic fatty acids and esters thereof canbe polymerized via non-catalytic polymerization at a higher temperature,or using catalysts such as acid or alkaline clays, di-t-butyl peroxide,boron, trifluoride and other Lewis acids, anthraquinone, sulfur dioxideand the like. Methods of dimerizing unsaturated fatty acids and theiresters are described in U.S. Pat. No. 6,187,903, among others. Suitablemonomers include linear or branched acids having at least oneethylenically unsaturated bond, such as about 2–5 of such bonds, like3-octenoic acid, 11-dodecanoic acid, linderic acid, oleic acid, linoleicacid, linolenic acid, hiragonic acid, eleostearic acid, punicic acid,catalpic acid, licanoic acid, clupadonic acid, clupanodonic acid,lauroleic acid, myristoleic acid, tsuzuic acid, palmitoleic acid,gadoleic acid, cetoleic acid, nervonic acid, moroctic acid, timmodonicacid, arachidonic acid (i.e., eicosatetraenoic acid), nisinic acid,scoliodonic acid, and chaulmoogric acid.

Acetylenically unsaturated monobasic fatty acids can be polymerized bysimply heating the acid. The polymerization of these highly reactivematerials can occur in the absence of a catalyst. Any acetylenicallyunsaturated fatty acid, linear or branched, mono-unsaturated orpoly-unsaturated, are useful monomers for the preparation of polymericfatty acids. Suitable examples of such materials include 10-undecynoicacid, tariric acid, stearolic acid, behenolic acid and isamic acid.

Polymerization reaction of the monobasic fatty acids as described above,include so-called dimeric fatty acids, are commonly structural isomermixtures containing a predominant proportion (about 45–95% by weight orgreater) of aliphatic and alicyclic dimer diacids (such as C₃₆ or C₄₄diacids), a small quantity (about 1–35% by weight) of trimer acids andhigher polymeric fatty acids (such as C₅₄₊ polyacids), and some (up toabout 20% by weight) residual monomers (such as C₁₈ or C₂₂ branchedchain monoacids). The ratio between the reactants in the disclosedprocess is known in the art as a topological ratio. Commercial productsof these polymeric fatty acids can contain about 75–95% by weight ofdimeric acids, about 4–22% by weight of trimeric acids, about 1–3% byweight of monomeric acid. The molar ratio of dimeric to trimeric acidcan be about 5:1 to about 36:1. The relative ratios of monomer, dimer,trimer and higher polymer in un-fractionated dimer acid can be dependenton the nature of the starting materials and the conditions ofpolymerization and subsequent distillation.

Dimerized fatty acids may be “crude”, i.e., obtained directly fromdimerization without distillation, or refined to increase dimerconcentration. Refined dimerized acids such as partially or fullyhydrogenated dimer fatty acids can have a dimer content of about 95% byweight or greater, such as at least about 97%, a monomer content ofabout 1%, a trimer content of about 3%, an acid value of about 193–201,a saponification value of about 198, and an iodine value of about 95.Hydrogenated dimer fatty acids can reduce aesthetically unpleasingcolor. The degree of hydrogenation can correspond to an iodine value ofabout 110 or less, such as about 95 or less, according to ASTM D1959-97or D5768-02. The fatty polyacids, such as the dimer diacids and diestersthereof, can be substantially free of interesters, the presence of whichmay hinder subsequent polymerization reactions. Methods for reducinginterester content in fatty polyacids include hydrolysis/extraction asdisclosed in U.S. Pat. No. 6,187,903, which is incorporated herein byreference. The fatty polyacids or esters thereof can have an interestercontent of about 0.2% by weight or less, such as about 0.05% or less.

Dimer diacids may be unsaturated, partly hydrogenated, or completelyhydrogenated (i.e., fully saturated). Non-limiting dimer diacids canhave one of the following structures:

where R is the same or different moieties chosen from hydrogen, alkyl,aryl, aralkyl, alicyclic, cycloalkyl, and alkoxy groups; x+y and m+n areboth at least about 8, such as at least about 10, such as 12, 14, 15,16, 18, 19, or greater.

Fatty polyacids can have at least one divalent hydrocarbon radicalhaving at least 30 carbon atoms, such as 36–180 carbon atoms, which canbe linear, branched, cyclic, and/or substituted, such asmonocycloaliphatic moiety having a 6-membered carbon ring (e.g.,cyclohexene ring), bicycloaliphatic moiety having a 10-membered carbonring, and substituted aliphatic moiety (e.g., halogenated aliphaticmoiety such as fluoroaliphatic polyacids). Fatty polyacids such as dimerdiacids can have an acid value of 150–250, such as 170–200 or 190–200, asaponification value of 170–210, and a viscosity at 25° C. of 50,000 cStor less, such as 30,000 cSt or less, 10,000 cSt or less, 500 cSt orgreater, like 600 cSt, 7,500 cSt, 8,500 cSt, 9,000 cSt, and anyviscosity therebetween. Examples are available from HumKo Chemical ofMemphis, Tenn. Fatty polyacids can be branched, such as with linear orbranched alkyl groups. Fluid fatty polyacids can be used as reactivediluents in solvent-borne polyurethane/polyurea compositions to achievehigher solid content.

Polymeric fatty acids and other polyacids as described above, as well asmethods to produce such polyacids can be found in U.S. Pat. Nos.6,670,429, 6,310,174, 6,187,903, 5,545,692, 5,326,815, 4,937,320,4,582,895, 4,536,339, and 4,508,652, among others. To form reactivepolymers of the present disclosure, polymeric fatty acids or estersthereof can also be epoxidized, for example by reaction with peraceticacid, performic acid or with hydrogen peroxide and formic acid or aceticacid. Suitable epoxidized fatty acids and esters are described inBritish Patent Nos. 810,348 and 811,797. Dimer acids can be converted todimer diols, dimer diamines, and/or dimer diisocyanates, all of whichare suitable for the compositions of the present disclosure.

Any and all amino acids known and/or available to one skilled in theart, which have at least one reactive amine group (such as primary aminegroup) and at least on acid group (such as carboxylic acid group), canbe used in the present disclosure. Also useful are cyclic amides of thecorresponding amino acids, and amino esters (such as methyl and ethylesters) of the corresponding amino acids. Any and all hydroxy acidsknown and/or available to one skilled in the art, which have at leastone reactive hydroxyl group and at least on acid group (such ascarboxylic acid group), are suitable for use in the present disclosure.Also useful are cyclic esters of the corresponding amino acids, andhydroxy esters (such as methyl and ethyl esters) of the correspondinghydroxy acids. Suitable amino acids, cyclic amides, amino esters,hydroxyl acids, cyclic esters, hydroxyl esters, cyclic ethers, and othercyclic compounds include, without limitation, those described in U.S.patent application Ser. Nos. 10/194,057, 10/409,144, and 10/859,527, andU.S. Pat. No. 6,835,794, the disclosures of which are incorporatedherein by reference in their entirety.

Any one or blend of two or more isocyanate-functional compoundsavailable to one of ordinary skill in the art may be suitable for use incompositions of the present disclosure. Isocyanate-functional compoundscan be organic isocyanates in general, and may have an isocyanatefunctionality of about 1 (i.e., monoisocyanates), such as about 2 orgreater (i.e., polyisocyanates). Polyisocyanates for use according tothe disclosure can include monomers, dimers (such as uretdiones ofidentical polyisocyanates and isocyanate derivatives of dimer acids ordimer amines), trimers (such as isocyanurates of identical or differentpolyisocyanates, isocyanate derivatives of trimer acids or trimeramines), tetramers, oligomers (oligoisocyanates and polyisocyanateswhich can be prepared from the diisocyanates, triisocyanates, orcombinations of two or more thereof, having one or more coupling meanssuch as urethane, allophanate, urea, biuret, uretdione, amide,isocyanurate, carbodiimide, uretonimine, oxadiazinetrione, and/oriminooxadiazinedione structures, and isocyanate derivatives of oligomerpolyacids or oligomer polyamines), adducts (such as uretdiones ofdifferent polyisocyanates and isocyanate derivatives of adduct polyacidsor adduct polyamines), polymers (such as isocyanate derivatives ofpolymer polyacids or polymer polyamines), polyisocyanate-terminatedprepolymers, low-free-isocyanate prepolymers, quasi-prepolymers, isomersthereof, modified derivatives thereof, and combinations of two or morethereof. Structure of the isocyanate reactant can partially or fully besubstituted, unsubstituted, saturated, unsaturated, hydrogenated,aliphatic, alicyclic, cyclic, polycyclic, aromatic, araliphatic,heteroaliphatic, and/or heterocyclic.

Exemplary polyisocyanates include, without limitation, those describedin U.S. patent application Ser. Nos. 10/194,057, 10/409,144, and10/859,527, and U.S. Pat. No. 6,835,794, the disclosures of which areincorporated herein by reference in their entirety. One or more or allof the reactable isocyanate groups-within the polyisocyanate compoundcan be sterically hindered, so that the polyisocyanate compound providethe combination of reduced reactivity toward active hydrogen groups suchas primary and secondary amines, and improved chemical stability towardactinic radiations such as UV light. The polyisocyanate can have NCOgroups of different reactivity, i.e., being regioselective. Reactantshaving high regioselectivity in general can enable efficient use inconsecutive reactions such as polymerization steps and crosslinking.They can provide cost advantages by reducing waste of functional groups(i.e., reduction in unreacted reactants), provide handling advantages byreducing volatile “leftover” molecules, and provide performanceadvantages by enabling controlled architecture in the reaction products(e.g., reduced polydispersity). Polyisocyanates can be derived from thefatty polyacids of the present disclosure. The fatty polyisocyanates canhave the same hydrocarbon structures as the fatty polyacids, except thateach COOH group is replaced by an NCO group. For example, dimer diacidscan be used to form saturated and/or unsaturated dimer diisocyanates.Dimer diisocyanates may be linear, branched (such as with linear orbranched alkyl groups), cyclic, and/or substituted, and can beunsaturated, partly hydrogenated, or completely hydrogenated (i.e.,fully saturated). Non-limiting dimer diisocyanates can have one of thefollowing structures:

where x+y and m+n are both at least about 8, such as at least about 10,such as 12, 13, 14, 15, 16, 17, 18, 19, or greater.

Fatty polyisocyanates can have at least one divalent hydrocarbon radicalhaving at least 30 carbon atoms, such as 36–180 carbon atoms, which canbe linear, branched, cyclic, and/or substituted, such asmonocycloaliphatic moiety having a 6-membered carbon ring (e.g.,cyclohexene ring), bicycloaliphatic moiety having a 10-membered carbonring, and substituted aliphatic moiety (e.g., halogenated aliphaticmoiety such as fluoroaliphatic polyisocyanates). Fatty polyisocyanatessuch as dimer diisocyanates are water insensitive, have controllablereactivity and low toxicity when compared to other aliphaticpolyisocyanates. The fatty polyisocyanates can have a % NCO content of20% or less, 15% or less, 10% or less, 5% or greater, or any amountstherebetween, such as 6–9%, 12–16%, 13–15%, or 13.6–14.3%. The fattypolyisocyanates can have a molecular weight of 250 or greater, such as500 or greater or 600 or greater, and up to about 15,000, such as about500–10,000. Fatty polyisocyanates can be liquid at room temperature,having low to moderate viscosity at 25° C. (e.g., about 100–10,000 cP orabout 500–5,000 cP). Other dimer diisocyanates are described in, forexample, Kirk-Othmer Encyclopedia of Chemical Technology 1979, volume 7,3^(rd) edition, p. 768–782, John Wiley and Sons, Inc., the disclosure ofwhich is entirely incorporated herein by reference.

Any and all of the compounds having two or more isocyanate-reactivefunctionalities as disclosed herein may be used as curatives to cureprepolymers into thermoplastic or thermoset compositions. Thesecuratives can be polyamines, polyols, aminoalcohols, polyaminetelechelics, and polyol telechelics, and aminoalcohol telechelics. Tofurther improve the shear resistance of the resulting elastomers,trifunctional curatives, tetrafunctional curatives, and higherfunctionality curatives can be used to increase crosslink density. Thesecompounds may have a molecular weight of 200 or greater, or 230 to3,000, or 230 to 1,000, or 230 to 500, such as 300, or 400, or anyranges between any two of such numbers. The curative may be modifiedwith a freezing point depressing agent to create a curative blend havinga slow onset of solidification and storage-stable pigment dispersion.Curatives comprising one or more ethylenic and/or acetylenicunsaturation moieties can be used to incorporate these moieties into theresulting material for subsequent crosslinking. Suitable curatives andblends of two or more thereof include, without limitation, thosedescribed in U.S. patent application Ser. Nos. 10/194,057, 10/409,144,and 10/859,527, U.S. Pat. Nos. 6,835,794, 5,484,870, and 4,808,691, thedisclosures of which are incorporated herein by reference in theirentirety.

The compositions of the disclosure may comprise at least one polyureaformed from the well-known one-shot method or prepolymer method. In thelatter, polyamine telechelic is reacted with excess polyisocyanate toform polyurea prepolymer, which is then reacted with curative to formthe polyurea. Prepolymer to curative ratio can be as high as 1:0.9 or1:0.95, such as when primary polyamine curatives are used, or as low as1:1.1 or 1:1.05, such as 1:1.02, such as when secondary polyaminecuratives are used. Curative includes polyamines, polyols, polyacids,aminoalcohols, aminoacids, and hydroxy acids, especially those disclosedherein, as well as epoxy-functional reactants, thio-containingreactants, and any other isocyanate-reactive compounds and materials.The polyurea composition can be castable, thermoplastic, thermoset, ormillable.

The polyurea prepolymer can be low-melting (such as being fluid at about125° C.) or fluid at ambient temperature. The content of reactableisocyanate moieties in the polyurea prepolymer, expressed as % NCO byweight, can be less than about 30%, such as about 15%, about 11%, about9%, about 7%, or even less, or at least about 2%, such as about 3% orabout 4% or greater, or any percentage therebetween, such as about5–11%, about 6–9.5%, about 3–9%, about 2.5–7.5%, or about 4–6.8%. Informing the polyurea prepolymer, polyamine telechelics as disclosedherein can be used alone or in combination of two or more thereof toreact with excess isocyanate. Prepolymers with higher % NCO (e.g., 14%)can be converted to prepolymers with lower % NCO (e.g., 10%) by furtherreacting with one or more other polyamines, polyols, polyaminetelechelics, and/or polyol telechelics. Polyurea prepolymers may containa content of free isocyanate monomers by about 1% or less of the totalweight, such as about 0.5% or less.

When forming a saturated prepolymer, such as for use in highlylight-stable compositions, saturated polyisocyanates being aliphatic,alicyclic, and/or heteroaliphatic can be used alone or in combinationsof two or more thereof. Araliphatic polyisocyanates, alone or inmixtures of two or more thereof, may also be used to form relativelylight-stable materials. Without being bound to any particular theory, itis believed that the direct attachment of the NCO moieties to aliphaticside chains without conjugation with the aromatic rings prevents thearaliphatic polyisocyanates from, or diminishes their ability in,forming extended conjugated double bonds, which may give rise todiscoloration (e.g., yellowing). The sterically hindered polyisocyanatesare useful in forming highly or relatively light-stable materials.Without being bound to any particular theory, it is believed that thesteric hinderance around the N atom tends to rotate it out of plane,thereby reducing its absorbance of UV wavelengths and achieving desiredlight-stability. Moreover, one or more of the NCO groups in thesterically hindered polyisocyanates can be attached to tertiary orquaternary carbon atoms that are substantially free of C—H bonds, thuseliminating or reducing the occurrence of UV-induced oxidation at thecarbon atoms, and in turn slowing degradation or discoloration. Thesaturated polyisocyanates, the araliphatic polyisocyanates, and thesterically hindered polyisocyanates may be used alone or in anycombinations of two or more thereof.

The compositions of the disclosure may comprise at least onepolyurethane, such as the reaction product of at least one polyurethaneprepolymer and at least one curative, of which the polyurethaneprepolymer is the reaction product of at least one polyol telechelic andat least one polyisocyanate. Prepolymer to curative ratio can be 1:0.9to 1:1.1, such as 1:0.95, 1:1.05, or 1: 1.02. One or more of the polyoltelechelic, the polyisocyanate, and the curative can be chosen fromthose disclosed herein, can be saturated, and the resulting polyurethanecan be saturated. Polyurethane prepolymers can have free isocyanatemonomers by about 1% or less of the total weight, such as about 0.5% orless. The polyurethane composition can be castable, thermoplastic,thermoset, or millable. The % NCO by weight in the prepolymer can beless than about 30%, such as about 15%, about 11%, about 9%, about 7%,or even less, or at least about 2%, such as about 3% or about 4% orgreater, or any percentage therebetween, such as about 5–11%, about6–9.5%, about 3–9%, about 2.5–7.5%, or about 4–6.8%. In forming thepolyurethane prepolymer, polyol telechelics as disclosed herein can beused alone or in combination of two or more thereof to react with excessisocyanate. Prepolymers with higher % NCO (e.g., 14%) can be convertedto prepolymers with lower % NCO (e.g., 10%) by further reacting with oneor more other polyamines, polyols, polyamine telechelics, and/or polyoltelechelics (e.g., polyamine polyamides, polyol polysiloxanes).

Crosslinkable polyurethanes can be formed from polyol telechelics,curatives, and stoichiometrically deficient amounts of polyisocyanatesuch as diisocyanate. Any one or more the reactants can have one or morealiphatic, non-benzenoid >C═C<moieties for crosslinking. Suchpolyurethanes can have rubber elasticity and wear resistance andstrength, and can be millable. Polyol telechelics of lowcrystallizability, such as those having linear or branched side chainsand those formed by random copolymerization (e.g, polyol polyethers,polyol polyesters, polyol polyetheresters, and others as disclosedherein), can be used to form such polyurethanes. Non-limiting examplesinclude polyethylene propylene adipate polyols, polyethylene butyleneadipate polyols, polytetramethylene ether glycols (such as those havingM_(w) of about 2,000), tetrahydrofuran (THF)-alkyl glycidyl ether randomcopolymers, and other polyol polyesters based on adipic acid and diolslike ethanediol, butanediol, methylpropanediol, hexanediol. Polyoltelechelics can be incorporated with ethylenic and/or acetylenicunsaturation moieties, such as by reacting them with α,β-ethylenicallyunsaturated carboxylic acids, and then crosslinked using vulcanizingagents.

Desired properties of crosslinkable polyurethanes include Mooneyviscosity at 100° C. of 40–70 (e.g., 50, 60, 65, or therebetween),tensile strength of 2,000–6,000 psi (e.g., 3,000 psi, 4,000 psi, 5,000psi, or therebetween), tear strength of 300–600 lb/in (e.g., 400 lb/in,500, lb/in, or therebetween), brittle point of −70° F. or lower (e.g.,−80° F., −90° F., or lower), material hardness of 25 Shore A to 60 ShoreD (e.g., 55 Shore D), elongation at break of 100–700% (e.g., 300%, 400%,500%, 600%, or therebetween), Bashore rebound of 40–70% (45%, 55%, ortherebetween), and abrasion index (ASTM D-1630) of 300 or greater.

The compositions of the disclosure may comprise at least onepoly(urethane-co-urea) formed from poly(urethane-co-urea) prepolymer andcurative. Prepolymer to curative ratio can be as high as 1:0.9 or1:0.95, such as when primary polyamine curatives are used, or as low as1:1.1 or 1:1.05, such as 1:1.02, such as when secondary polyaminecuratives are used. Curative includes polyamines, polyols, polyacids,aminoalcohols, aminoacids, and hydroxy acids, especially those disclosedherein, as well as epoxy-functional reactants, thio-containingreactants, and any other isocyanate-reactive compounds and materials.Poly(urethane-co-urea) prepolymer refers to isocyanate-functionalprepolymer having at least one urethane linkage and at least one urealinkage in the backbone. Such a prepolymer is distinct from polyurethaneprepolymer, polyurea prepolymer, and blends thereof. Thepoly(urethane-co-urea) prepolymer can be formed by reacting excessisocyanate with a blend of at least one polyamine telechelic and atleast one polyol telechelic. Molar ratio of polyol telechelic topolyamine telechelic in the blend can be about 0.5:1 to about 10:1, suchas about 0.6:1 to about 7:1. Examples of blend include polyether polyolssuch as polyoxytetramethylene diol and polyether polyamines such aspolyoxypropylene diamine.

The poly(urethane-co-urea) composition can be castable, thermoplastic,thermoset, or millable. The % NCO by weight in the prepolymer can beless than about 30%, such as about 15%, about 11%, about 9%, about 7%,or even less, or at least about 2%, such as about 3% or about 4% orgreater, or any percentage therebetween, such as about 5–11%, about6–9.5%, about 3–9%, about 2.5–7.5%, or about 4–6.8%. Prepolymers withhigher % NCO (e.g., 14%) can be converted to prepolymers with lower %NCO (e.g., 10%) by further reacting with one or more other polyamines,polyols, polyamine telechelics, and/or polyol telechelics (e.g.,polyamine polyamides, polyol polysiloxanes). The poly(urethane-co-urea)prepolymer can be formed by reacting excess isocyanate with anaminoalcohol telechelic (or a blend of two or more thereof), optionallymixed with at least one polyamine reactant and/or at least one polyolreactant. The poly(urethane-co-urea) prepolymer can also be formed byreacting excess isocyanate with a polyamine reactant having at least oneurethane linkage in the backbone, or with a polyol reactant having atleast one urea linkage in the backbone. Polyamine reactants include anyone or more polyamine telechelics and polyamines disclosed herein.Polyol reactants include any one or more polyol telechelics and polyolsdisclosed herein. The poly(urethane-co-urea) prepolymer can further beformed in situ from a mixture of at least one polyisocyanate, at leastone cyclic compound such as cyclic ether, and at least one telechelicchosen from polyamine telechelics, polyol telechelics, and aminoalcoholtelechelics as disclosed herein.

The reactive compositions of the present disclosure can be covalentlyincorporated or functionalized with ionic groups or precursor groupsthereof, which can impart desirable properties to the resulting polymermaterials. The term “ionic group or precursor group thereof” means agroup either already in an anionic or cationic form or else, byneutralization with a reagent, readily converted to the anionic orcationic form respectively. The term “neutralize” as used herein forconverting precursor groups to ionic groups refers not only toneutralization using true acids and bases but also includesquaternarization and ternarization. Illustrative of precursor anionicgroups (and neutralized form) are acid groups like carboxylic group—COOH(—COO^(⊖)), sulfonic group —SO₂OH(—SO₂O^(⊖)), and phosphoric group(i.e., ═POOH or ═POO^(⊖)); illustrative of precursor cationic groups(and neutralized form) are ≡N(≡N—^(⊕)), ≡P(≡P—^(⊕)), and ═S(═S—^(⊕)).

The precursor groups of ionic groups can be incorporated into theisocyanate-reactive telechelic (including polyamine telechelics, polyoltelechelics, and aminoalcohol telechelics), the isocyanate, and/or thecurative before, during, or after the prepolymer formation or the curingreaction. They can be neutralized to corresponding ionic groups before,during, or after the prepolymer formation or the curing reaction. Forexample, the acid groups may be neutralized to form the correspondingcarboxylate anion, sulfonate anion, and phosphate anion by treatmentwith inorganic or organic bases. Cationic precursor groups such astertiary amine, phosphine, and sulfide groups can be neutralized byneutralization or quaternarization of the tertiary amine, or reactingthe phosphine or sulfide with compounds capable of alkylating thephosphine or sulfide groups.

Suitable inorganic bases used for partial or total neutralization mayinclude ammonia, oxides, hydroxides, carbonates, bicarbonates andacetates. Cation for the inorganic base can be ammonium or metal cationssuch as, without limitation, Group IA, IB, IIA, IIB, IIIA, IIIB, IVA,IVB, VA, VB, VIA, VIB, VIIB and VIIIB metal ions, which include, withoutlimitation, lithium, sodium, potassium, magnesium, zinc, calcium,cobalt, nickel, tin, iron, copper, manganese, aluminum, tungsten,zirconium, titanium and hafnium. Suitable organic bases used for partialor full neutralization can be hindered organic tertiary amines such astributylamine, triethylamine, tripropylamine, triethylene diamine,dimethyl cetylamine and similar compounds. Primary or secondary aminesmay be used, such as if the neutralization takes place after the polymeris formed, because the amine hydrogen can react with the isocyanategroups thereby interfering with the polyurea or polyurethanepolymerization. One of ordinary skill in the art is aware of additionalappropriate chemicals for neutralization.

At least a portion of the ionic groups can be covalently incorporatedinto the isocyanate-reactive telechelic before prepolymer formation.Suitable acid functional isocyanate-reactive telechelics may have anymolecular weight, such as 1,500, an acid number (calculated by dividingacid equivalent weight to 56,100) of at least about 5, such as at leastabout 10, at least about 25, at least about 30, or at least about 50,may be about 420 or less, such as about 200 or less, about 150 or less,about 100 or less, and an acid functionality of greater than 1, such as1.4 or greater. In the case of polyol telechelics, the hydroxyl number(unit being mg KOH/g) of the polyols may be at least about 10, or 20 orgreater, or 30 or greater, or 50 or greater, or 65 or greater,preferably 840 or less, or 300 or less, or 200 or less, or 150 or less,or 100 or less, or 80 or less, or 65 or less, or any rangestherebetween, such as 28 to 112, or 187 to 560. The polyol telechelicsmay also have a hydroxyl functionality (average number of hydroxylgroups per polyol molecule) of greater than 1, about 2 or greater, like1.8, and up to about 4. The acid functional telechelic can be liquid orwax at ambient temperature, and can have a viscosity at 60° C. of lessthan 5,000 cP, or 3,000 cP or less, such as 2,700 cP or less. Ionicgroups or precursor groups thereof may be incorporated in ways thatinclude, without limitation, those described in U.S. patent applicationSer. No. 10/859,527, the disclosure of which is incorporated herein byreference in its entirety.

Additional materials may be incorporated into any of the reactivecompositions of the present disclosure, or any one or more of thereactive subcomponents thereof. These additives include, but are notlimited to, catalysts to alter the reaction rate, fillers to adjustdensity and/or modulus, processing aids or oils (such as reactive ornon-reactive diluents) to affect rheological and/or mixing properties,reinforcing materials, impact modifiers, wetting agents, viscositymodifiers, release agents, internal and/or external plasticizers,compatibilizing agents, coupling agents, dispersing agents, crosslinkingagents, defoaming agents, surfactants, lubricants, softening agents,coloring agents including pigments and dyes, optical brighteners,whitening agents, UV absorbers, hindered amine light stabilizers,blowing agents, foaming agents, and any other modifying agents known oravailable to one of ordinary skill in the art. One or more of theseadditives are used in amounts sufficient to achieve their respectivepurposes and desired-effects. Suitable additives include, include,without limitation, those described in U.S. patent application Ser. Nos.10/194,057, 10/409,144, and 10/859,527, and U.S. Pat. No. 6,835,794, thedisclosures of which are incorporated herein by reference in theirentirety.

The compositions of the disclosure can be used in amounts of 1–100%,such as 10–90% or 10–75%, to form any portion of the golf ball,optionally in blend with one or more other materials being present inamounts of 1–95%, 10–90%, or 25–90%. The percentages are based on theweight of the portion in question. Conventional materials for golf ballcover, intermediate layer, and core suitable as the other materialsinclude, without limitation, those described in U.S. patent applicationSer. Nos. 10/194,057, 10/409,144, and 10/859,527, and U.S. Pat. No.6,835,794, the disclosures of which are incorporated herein by referencein their entirety.

The cores of the golf balls formed according to the disclosure may besolid, semi-solid, hollow, fluid-filled, gas-filled, powder-filled,one-piece or multi-component cores. The term “semi-solid” as used hereinrefers to a paste, a gel, or the like. Any core material known to one ofordinary skill in that art is suitable for use in the golf balls of thedisclosure. Suitable core materials include thermoset materials, such asrubber, styrene butadiene, polybutadiene, isoprene, polyisoprene,trans-isoprene, as well as thermoplastics such as ionomer resins,polyamides, and polyesters, and thermoplastic or thermoset polyurethaneor polyurea elastomers. As mentioned above, the compositions of thepresent disclosure may be incorporated into any portion of the golfball, including the core. For example, an inner core center or a corelayer may comprise at least one of the reactive compositions disclosedherein.

The golf ball core can comprise one or more materials chosen from baserubber (natural, synthetic, or a combination thereof, such aspolybutadiene), crosslinking initiator (such as dialkyl peroxide),co-crosslinking agent (such as those having di- or polyunsaturation andat least one readily extractable hydrogen in the α position to theunsaturated bonds), filler, cis-to-trans catalyst, organosulfurcompound, among others. Choices for these materials are known to oneskilled in the art, such as those disclosed in co-pending andco-assigned U.S. Patent Publication No. 2003/0119989, bearing Ser. No.10/190,705, the disclosure of which is incorporated by reference herein.The core compositions can be used to form any other portions of the golfball, such as one or more of the intermediate layers and cover layers.

When the golf ball comprises at least one intermediate layer, such asone disposed between the cover and the core, or an inner cover layer orouter core layer, i.e., any layer(s) disposed between the inner core andthe outer cover of the golf ball, this layer can be formed from any oneor more thermoplastic and thermosetting materials known to those ofordinary skill. These materials can be any and all of the compositionsdisclosed herein, and include, without limitation, those described inU.S. patent application Ser. Nos. 10/194,057, 10/409,144, and10/859,527, and U.S. Pat. No. 6,835,794, the disclosures of which areincorporated herein by reference in their entirety. One or more of suchintermediate layers may be moisture barrier layers, such as the onesdescribed in U.S. Pat. No. 5,820,488, which is incorporated by referenceherein.

One or more of the cover layers may be formed, at least in part, fromthe compositions of the present disclosure. The cover layers includeouter cover layer, inner cover layer, and any intermediate layerdisposed between the inner and outer cover layers. The covercompositions can include one or more of the polyurethane prepolymers,polyurea prepolymers, poly(urethane-co-urea) prepolymers,polyisocyanates, curatives, and additives. Other materials useful incover composition blends include those disclosed herein for the core andthe intermediate layer.

The golf ball can have any construction, including, but not limited to,one-piece, two-piece, three-piece, four-piece, and other multi-piecedesigns. The golf ball can have a single core, a 2-layer core, a 3-layercore, a 4-layer core, a 5-layer core, a 6-layer core, a multi-layercore, a single cover, a 2-layer cover, a 3-layer cover, a 4-layer cover,a 5-layer cover, a 6-layer cover, a multi-layer cover, a multi-layercover, and/or one or more intermediate layers. The compositions of thedisclosure may be used in any one or more of these golf ball portions,each of which may have a single-layer or multi-layer structure. As usedherein, the term “multi-layer” means at least two layers. Any of theseportions can be one of a continuous layer, a discontinuous layer, awound layer, a molded layer, a lattice network layer, a web or net, anadhesion or coupling layer, a barrier layer, a layer of uniformed ornon-uniformed thickness, a layer having a plurality of discrete elementssuch as islands or protrusions, a solid layer, a metallic layer, aliquid-filled layer, a gel-filled portion, a powder-filled portion, agas-filled layer, a hollow portion, or a foamed layer.

In addition, when the golf ball of the present disclosure includes anintermediate layer, this layer may be incorporated with a single ormultilayer cover, a single or multi-piece core, with both a single layercover and core, or with both a multilayer cover and a multilayer core.The intermediate layer may be an inner cover layer or outer core layer,or any other layer(s) disposed between the inner core and the outercover of a golf ball. As with the core, the intermediate layer may alsoinclude a plurality of layers. It will be appreciated that any number ortype of intermediate layers may be used, as desired. The intermediatelayer may also be a tensioned elastomeric material wound around a solid,semi-solid, hollow, fluid-filled, or powder-filled center. As usedherein, the term “fluid” refers to a liquid or gas and the term“semi-solid” refers to a paste, gel, or the like. A wound layer may bedescribed as a core layer or an intermediate layer for the purposes ofthe disclosure. The would layer may be formed from a composition of thedisclosure having at least one hydrophobic backbone or segment forimproved water resistance.

The golf balls of the disclosure may be formed using a variety ofapplication techniques such as compression molding, flip molding,injection molding, retractable pin injection molding, reaction injectionmolding (RIM), liquid injection molding (LIM), casting, vacuum forming,powder coating, flow coating, spin coating, dipping, spraying, and thelike. Detailed descriptions of these methods are known to one skilled inthe art, and can be found in U.S. patent application Ser. Nos.10/194,057, 10/409,144, and 10/859,527, and U.S. Pat. No. 6,835,794, aswell as references cited therein, the disclosures of which areincorporated herein by reference in their entirety.

The use of various dimple patterns and profiles provides a relativelyeffective way to modify the aerodynamic characteristics of a golf ball.As such, the manner in which the dimples are arranged on the surface ofthe ball can be by any available method. Non-limiting dimple patternsinclude icosahedral, octahedral, phyllotactic, and Archimedean withnon-linear parting line, including truncated octahedron, greatrhombcuboctahedron, truncated dodecahedron, and greatrhombicosidodecahedron. The dimples can be circular and/or non-circular,such as amorphous, have tubular lattice pattern, having catenarycurvature, have varying sizes, and/or have high percentage of surfacecoverage.

The golf balls of the present disclosure may be painted, coated, orsurface treated for further advantages. The use of light stable reactivecompositions may obviate the need for certain post-processing such asapplying pigmented coating or clear topcoat, thus reducing cost andproduction time, reducing use of volatile organic compounds (VOCs), andimproving labor efficiency. Toning the golf ball cover with titaniumdioxide can enhance its whiteness. The cover can be subjected to suchsurface treatment as corona treatment, plasma treatment, UV treatment,flame treatment, electron beam treatment, and/or applying one or morelayers of clear paint, which optionally may contain one or morefluorescent whitening agents. Trademarks and/or other indicia may bestamped, i.e., pad-printed, on the cover, and then covered with one ormore clear coats for protection and glossy look. UV treatment can beused to cure UV-curable topcoat and/or ink layer (used as a paint layeror a discrete marking tool for logo and indicia).

Physical properties of each golf ball portion, such as hardness,modulus, compression, and thickness/diameter, can affect playcharacteristics-such as spin, initial velocity, and feel. It should beunderstood that the ranges herein are meant to be intermixed with oneanother, i.e., the low end of one range may be combined with the highend of another range. Suitable ranges for these and other properties aredescribed in U.S. patent application Ser. Nos. 10/194,057, 10/409,144,and 10/859,527, and U.S. Pat. No. 6,835,794, the disclosures of whichare incorporated herein by reference in their entirety.

Golf balls and portions thereof of the present disclosure can have anydimensions, i.e., thickness and/or diameter. While USGA specificationslimit the size of a competition golf ball to 1.68 inches or greater indiameter, golf balls of any sizes smaller or larger can be used forleisure play. As such, the golf ball diameter can be 1.68–1.8 inches,1.68–1.76 inches, 1.68–1.74 inches, or 1.7–1.95 inches. Golf ballsubassemblies comprising the core and one or more intermediate layerscan have a diameter of 80–98% of that of the finished ball. The core mayhave a diameter of 0.09–1.65 inches, such as 1.2–1.63 inches, 1.3–1.6inches, 1.4–1.6 inches, 1.5–1.6 inches, or 1.55–1.65 inches.Alternatively, the core diameter can be 1.54 inches or greater, such as1.55 inches or greater, or 1.59 inches or greater, and 1.64 inches orless. The core diameter can be 90–98% of the ball diameter, such as94–96%. When the core comprises an inner center and at least one outercore layer, the inner center can have a diameter of 0.9 inches orgreater, such as 0.09–1.2 inches or 0.095–1.1 inches, and the outer corelayer can have a thickness of 0.13 inches or greater, such as 0.1–0.8inches, or 0.2 or less, such as 0.12–0.01 inches or 0.1–0.03 inches.Two, three, four, or more of outer core layers of different thicknesssuch as the ranges above may be used in combination.

Thickness of the intermediate layer may vary widely, because it can beany one of a number of different layers, e.g., outer core layer, innercover layer, wound layer, and/or moisture/vapor barrier layer. Thethickness of the intermediate layer can be 0.3 inches or less, such as0.1 inches, 0.09 inches, 0.06 inches, 0.05 inches, or less, and can be0.002 inches or greater, such as 0.01 inches or greater. Theintermediate layer thickness can be 0.01–0.045 inches, 0.02–0.04 inches,0.025–0.035 inches, 0.03–0.035 inches. Two, three, four, or more ofintermediate layers of different thickness such as the ranges above maybe used in combination. The core and intermediate layer(s) together forman inner ball, which can have a diameter of 1.48 inches or greater, suchas 1.5 inches, 1.52 inches, or greater, or 1.7 inches or less, such as1.66 inches or less.

The cover thickness can be 0.35 inches or less, such as 0.12 inches, 0.1inches, 0.07 inches, or 0.05 inches or less, and 0.01 inches or greater,such as 0.02 inches or greater. The cover thickness can be 0.02–0.05inches, 0.02–0.045 inches, or 0.025–0.04 inches, such as about 0.03inches. Thickness ratio of the intermediate layer (e.g., as an innercover layer) to the cover (e.g., as an outer cover layer) can be 10 orless, such as 3 or less, or 1 or less.

Golf balls can comprise layers of different hardness, e.g., hardnessgradients, to achieve desired performance characteristics. The hardnessof any two adjacent or adjoined layers can be the same or different. Oneof ordinary skill in the art understands that there is a differencebetween “material hardness” and “hardness, as measured directly on agolf ball.” Material hardness is defined by the procedure set forth inASTM-D2240 and generally involves measuring the hardness of a flat“slab” or “button” formed of the material in question. Hardness, whenmeasured directly on a golf ball (or other spherical surface) isinfluenced by a number of factors including, but not limited to, ballconstruction (i.e., core type, number of core and/or cover layers,etc.), ball (or sphere) diameter, and the material composition ofadjacent layers, and can therefore be different from the materialhardness. The two hardness measurements are not linearly related and,therefore, cannot easily be correlated.

The cores of the present disclosure may have varying hardness dependingat least in part on the golf ball construction. The core hardness asmeasured on a formed sphere can be at least 15 Shore A, such as at least30 Shore A, about 50 Shore A to about 90 Shore D, about 80 Shore D orless, about 30–65 Shore D, or about 35–60 Shore D. The intermediatelayer(s) of the present disclosure may also vary in hardness, dependingat least in part on the ball construction. The hardness of theintermediate layer can be about 30 Shore D or greater, such as about 50Shore D or greater, about 55 Shore D or greater, or about 65 Shore D orgreater, and can be about 90 Shore D or less, such as about 80 Shore Dor less or about 70 Shore D or less, or about 55–65 Shore D. Theintermediate layer can be harder than the core layer, having a ratio ofhardness of about 2 or less, such as about 1.8 or less, or about 1.3 orless. The intermediate layer can be different (i.e., harder or softer)than the core layer with a hardness difference of at least 1 unit inShore A, C, or D, such as at least 3 units, or at least 5 units, or atleast 8 units, or at least 10 units, or less than 20 units, or less than10 units, or less than 5 units.

The hardness of the cover layer may vary, depending at least in part onthe construction and desired characteristics of the golf ball. On theShore C scale, the cover layer may have a hardness of about 70 Shore Cor greater, such as about 80 Shore C or greater, and about 95 Shore C orless, such as about 90 Shore C or less.

The difference or ratio of hardness between the cover layer and theinner ball can be manipulated to influence the aerodynamics and/or spincharacteristics of a ball. When the intermediate layer (such as innercover layer) is at least harder than the cover layer (such as outercover layer), or intended to be the hardest portion in the ball, e.g.,about 50–75 Shore D, the cover layer may have a material hardness ofabout 20 Shore D or greater, such as about 25 Shore D or greater, orabout 30 Shore D or greater, or the cover hardness as measured on theball can be about 30 Shore D or greater, such as about 30–70 Shore D,about 40–65 Shore D, about 40–55 Shore D, less than about 45 Shore D,less than about 40 Shore D, about 25–40 Shore D, or about 30–40 Shore D.The material hardness ratio of softer layer to harder layer can be about0.8 or less, such as about 0.75, about 0.7, about 0.5, about 0.45, orless. When the intermediate layer and the cover layer have substantiallythe same hardness, the material hardness ratio can be about 0.9 orgreater, and up to 1.0, and the cover layer may have a hardness of about55–65 Shore D. Alternatively, the cover layer can be harder than theintermediate layer, with the hardness ratio of the cover layer to theintermediate layer being about 1.33 or less, such as about 1.14 or less.

The core may be softer than the cover. For example, the cover hardnessmay be about 50–80 Shore D, and the core hardness may be about 30–50Shore D, with the hardness ratio being about 1.75 or less, such as about1.55 or less or about 1.25 or less.

As used herein, the terms “Atti compression” or “compression” refers tothe deflection of an object or material relative to the deflection of acalibrated spring, as measured with an Atti Compression Gauge availablefrom Atti Engineering Corp. of Union City, N.J. Compression values ofthe golf ball or portion thereof can be at least in part dependent onthe diameter. Atti compression of the core or portion thereof can be 80or less, such as 75 or less, 40–80, 50–70, 50 or less, 25 or less, 20 orless, 10 or less, or 0, or below the measurable limit of the AttiCompression Gauge. The core or portion thereof may have a Soft CenterDeflection Index (SCDI) compression of 160 or less, such as 40–160 or60–120. The golf ball can have an Atti compression of 40 or greater,such as 55 or greater, 50–120, 60–120, 50–120, 60–100, 75–95, or 80–95.

USGA limits the initial velocity of a golf ball up to 250±5 ft/s. Theinitial velocity of the golf ball of the present disclosure can be245–255 ft/s, or greater, such as 250 ft/s or greater, 253–254 ft/s, orabout 255 ft/s. Coefficient of restitution (COR) of a ball or a portionthereof is measured by taking the ratio of the outbound or reboundvelocity to the inbound or incoming velocity (such as, but not limitedto, 125 ft/s). COR can be maximized so that the initial velocity iscontained with a certain limit. COR of the golf ball can be 0.7 orgreater at an inbound velocity of 125 ft/s, such as 0.75 or greater,0.78 or greater, 0.8 or greater, and up to about 0.85, such as0.8–0.815. The core and/or the inner ball can have a COR of 0.78 ormore, such as 0.79 or greater, or 0.8 or greater.

As used herein, the term “flexural modulus” or “modulus” refers to theratio of stress to strain within the elastic limit (measured in flexuralmode) of a material, indicates the bending stiffness of the material,and is similar to tensile modulus. Flexural modulus, typically reportedin Pascal (“Pa”) or pounds per square inch (“psi”), is measured inaccordance to ASTM D6272–02.

The intermediate layer (e.g., outer core layer, inner cover layer) canhave any flexural modulus of 500–500,000 psi, such as 1,000–250,000 psior 2,000–200,000 psi. The flexural modulus of the cover layer (e.g.,outer cover layer, inner cover layer, intermediate cover layer) can be2,000 psi or greater, such as 5,000 psi or greater, 10,000–150,000 psi,15,000–120,000 psi, 18,000–110,000 psi, 100,000 psi or less, 80,000 orless, 70,000 psi or less, 10,000–70,000 psi, 12,000–60,000 psi, or14,000–50,000 psi.

The cover layer (e.g., inner cover, intermediate cover, outer coverlayers) can have any flexural modulus, such as the numerical rangesillustrated for intermediate layer above. When the cover layer has ahardness of 50–60 Shore D, the flexural modulus can be 55,000–65,000psi. In multi-layer covers, the cover layers can have substantially thesame hardness but different flexural moduli. The difference in flexuralmodulus between any two cover layers can be 10,000 psi or less, 5,000psi or less, or 500 psi or greater, such as 1,000–2,500 psi. The ratioin flexural modulus of the intermediate layer to the cover layer can be0.003–50, such as 0.006–4.5 or 0.11–4.5.

The specific gravity of a cover or intermediate layer can be at least0.7, such as 0.8 or greater, 0.9 or greater, 1 or greater, 1.05 orgreater, or 1.1 or greater. The core may have a specific gravity of 1 orgreater, such as 1.05 or greater. In one example, the intermediate layerhas a specific gravity of 0.9 or greater and the cover has a specificgravity of 0.95 or greater. In another example, the core specificgravity is 1.1 or greater and the cover specific gravity is about 0.95or greater.

The adhesion, or peel, strength of the compositions as presentlydisclosed can be 5 lb_(f)/in or greater, such as 10 lb_(f)/in orgreater, 20 lb_(f)/in or greater, 24 lb_(f)/in or greater, or 26 lb/inor greater, or 30 lb_(f)/in or less, such as 25 lb_(f)/in, 20 lb_(f)/in,or less. Adhesion strength of a golf ball layer can be assessed usingcross-hatch test (i.e., cutting the material into small pieces inmutually perpendicular directions, applying a piece of adhesivecellophane tape over the material, rapidly pulling off the tape, andcounting the number of pieces removed).

Water resistance of a golf ball portion can be reflected by absorption(i.e., weight gain following a period of exposure at a specifictemperature and humidity differential) and transmission (i.e., watervapor transmission rate (WVTR) according to ASTM E96-00, which refers tothe mass of water vapor that diffuses into a material of a giventhickness per unit area per unit time at a specific temperature andhumidity differential). The golf ball or a portion thereof can have aweight gain of 0.15 g or less, such as 0.13 g, 0.09 g, 0.06 g, 0.03 g,or less, and a diameter gain of 0.001 inches or less, over seven weeksat 100% relative humidity and 72° F. The golf ball portion such as theouter or inner cover layer can have a WVTR of 2 g/(m²×day) or less, suchas 0.45–0.95 g/(m²×day), 0.01–0.9 g/(m²×day), or less, at 38° C. and 90%relative humidity. Alternatively, the layer may have a WVTR of of 1g·mm/(m²·day) or less, or 0.65 g·mm/(m²·day) or less, or 0.4g·mm/(m²·day) or less, or 0.2 g·mm/(m²·day) or less, or 0.1g·mm/(m²·day) or less.

The shear/cut resistance of a golf ball portion (e.g., inner or outercover layer) may be determined using a shear test having a scale from 1to 6 in damage and appearance. The cover layer can have a number of 3,2, 1, or less on the shear test scale.

Light stability (such as to UV irradiance power of 1.00 W/m²/nm) of thecover layer (e.g., a visible layer such as an outer cover layer or aninner/intermediate cover layer having transparent or translucent outercover layers) may be quantified using difference in yellowness index(ΔYI, according to ASTM D1925) before and after a predetermined period(such as 120 hrs) of exposure. The ΔYI of the cover layer can be 10 orless. Difference in yellow-to-blue chroma dimension before and after theexposure (Δb*) can also quantify light stability. The Δb* of the coverlayer can be 5 or less, or 4 or less.

EXAMPLES

The following non-limiting examples are included herein merely forillustration, and are not to be construed as limiting the scope of thepresent disclosure. Golf balls were made having polyurethane coverscomprising prepolymers of H₁₂MDI and dimer acid-based polyester polyols,cured with polycaprolactone triols (molecular weight of 300). Propertiesand performance results in comparison with aromatic polyurethane coveredcontrol golf balls are listed below.

TABLE 1 DIMER ACID-BASED POLYESTER POLYOL POLYURETHANE GOLF BALL COVERSControl Example 1 Example 2 Formulations Isocyanate MDI H₁₂MDI H₁₂MDITelechelic PTMEG¹ Priplast ® 1838² Priplast ® 3196³ Curative Ethacure ®300⁴ PCL triol⁵ PCL triol Compression 85 87 84 Shore D Hardness 48 60 50COR @ 125 ft/s 0.806 0.804 0.802 Durability @ 400 hits No failures Nofailures No failures Cold Crack Test @ 5° F., 15 hits No failures Nofailures No failures Light Stability ΔYI — 7.07 8.22 (8 Days QUV) Δb* —4.03 4.67 ¹Polytetramethylene ether glycol with Mw of 2,000. ²Liquidpolyester polyol with Mw of 2,000 and OH value of 52–60, from Uniqema ofNew Castle, DE. ³Liquid polyester polyol with Mw of 3,000 and OH valueof 34–40, from Uniqema of New Castle, DE. ⁴Dimethylthiotoluene diamine,from Albemarle Corporation of Baton Rouge, LA. ⁵Polycaprolactone triolwith Mw of 300.

The forgoing disclosure and the claims below are not to be limited inscope by the illustrative examples presented herein. Any equivalentexamples are intended to be within the scope of this disclosure. Forexample, while disclosure is directed mainly to compositions for use ingolf balls, the same compositions may be used in other golf equipmentsuch as putters (e.g., as inserts or in the grip), golf clubs andportions thereof (e.g., heads, shafts, or grips), golf shoes andportions thereof, and golf bags and portions thereof. Indeed, variousmodifications of the disclosure in addition to those shown and describedherein will become apparent to those skilled in the art from theforegoing description. Such modifications are also intended to fallwithin the scope of the appended claims. Disclosures of relevant subjectmatters in all patents, applications, and publications as cited in theforegoing disclosure are expressly incorporate herein by reference intheir entirety.

1. A golf ball comprising a core and at least one layer disposed aboutthe core, wherein the layer comprises a composition comprising apolyester polyol formed from a polyol and a polyacid, and wherein atleast one of the polyol and the polyacid is a fatty compound.
 2. Thegolf ball of claim 1, wherein the polyacid is a fatty polyacidcomprising suberic acid, azelaic acid, sebacic acid, undecanedioic acid,dodecanedioic acid, brassylic acid, tetradecanedioic acid,pentadecanedioic acid, heptadecanedioic acid, heptadecanedioic acid,octadecanedioic acid, heptadecanedicarboxylic acid,octadecanedicarboxylic acid, nonadecanedicarboxylic acid,eicosanedicarboxylic acid, hydrogenated vinyl-tetradecenedioic acid,hydrogenated eicosedienedioic acid, hydrogenateddimethyl-eicosedienedioic acid, hydrogenated 8-vinyl-10-octadecenedioicacid, or a polymerized fatty polyacid.
 3. The golf ball of claim 1,wherein the polyacid comprises a dimer diacid, a trimer triacid, or anadduct diacid.
 4. The golf ball of claim 1, wherein the polyacid has astructure of:

where R comprises hydrogen, alkyl, aryl, aralkyl, alicyclic, cycloalkyl,or alkoxy group; m+n≧8; and x+y≧8.
 5. The golf ball of claim 1, whereinthe polyol is a fatty polyol.
 6. The golf ball of claim 1, wherein thepolyol is a dimer diol.
 7. The golf ball of claim 1, wherein the polyolhas a structure of:

where R comprises hydrogen, alkyl, aryl, aralkyl, alicyclic, cycloalkyl,or alkoxy group; m+n≧8; and x+y≧8.
 8. The golf ball of claim 1, whereinthe polyester polyol is formed from at least one dimer diol and at leastone dimer diacid.
 9. The golf ball of claim 1, wherein the polyesterpolyol has a molecular weight of 1,000 to 3,000.
 10. The golf ball ofclaim 1, wherein the polyester polyol has a hydroxyl number of 20 to150.
 11. The golf ball of claim 1, wherein the polyester polyol has ahydroxyl number of 30 to
 80. 12. The golf ball of claim 1, wherein thecomposition further comprises a polyisocyanate.
 13. The golf ball ofclaim 12, wherein the polyisocyanate and the polyester polyol react toform a prepolymer having a % NCO of 3% to 15%.
 14. The golf ball ofclaim 1, wherein the composition further comprises a triol or a tetraol.15. The golf ball of claim 1, wherein the composition further comprisesa polycaprolactone triol having a molecular weight of 230 to 1,000. 16.The golf ball of claim 1, wherein the layer is an outer cover layer. 17.The golf ball of claim 1, wherein the layer is an intermediate layerdisposed between the core and an outer cover layer.
 18. The golf ball ofclaim 1, wherein the layer is a coating layer.
 19. A golf ball, the golfball having a compression of 50 to 120 and comprising: a core, the corehaving a diameter of 1.5 inches to 1.65 inches; an intermediate layerdisposed about the core, the intermediate layer having a first Shore Dhardness of 20 to 80; an outer cover layer disposed about theintermediate layer; the outer cover layer having a thickness of 0.005inches to 0.05 inches and a second Shore D hardness of 30 to 70; and anoptional coating layer disposed about the outer cover layer, wherein atleast one of the intermediate layer, the outer cover layer, and thecoating layer is formed from a composition comprising a polyester polyolformed from a dimer diol and a dimer diacid, a polyisocyanate, and atriol or tetraol.
 20. The golf ball of claim 19, wherein the core or thegolf ball has a coefficient of restitution of 0.8 or greater.